Decorative film or sheet, and decorative material and building material made by using the same

ABSTRACT

A decorative film or sheet having a laminate structure comprising a surface layer, an adhesive layer, and a layer having a pattern or a laminate structure comprising a surface layer, an adhesive layer, a layer having a pattern, an adhesive layer, and a substrate, wherein the surface layer is made of a film of a sheet comprising a resin which comprises (A) 100 to 60% by weight of a substantial homopolymer of polypropylene having a pentad fraction, a peak temperature of melting, and an enthalpy of melting each in a specific range and (B) 0 to 40% by weight of a thermoplastic elastomer copolymer and a decorative building material having a surface layer made of a film or a sheet comprising the above resin. In accordance with the present invention, a laminated decorative film or sheet which comprises a surface layer having excellent transparency and hardness, has excellent workability in bending, V-cutting, lapping, and vacuum molding, and does not cause problems in disposal and a decorative building material which has excellent heat resistance, weatherability, and abrasion resistance, provides soft feeling, and does not cause problems in the environment can be obtained easily.

TECHNICAL FIELD

The present invention relates to a decorative film or sheet, adecorative material comprising the same, and a decorative buildingmaterial comprising the same. More particularly, the present inventionrelates to a laminated decorative film or sheet which comprises asurface layer having excellent transparency and hardness, has excellentworkability in bending, V-cutting, lapping, and vacuum molding, and doesnot cause problems in disposal because chlorine gas is not formed byincineration, a decorative material comprising this decorative film orsheet, and a decorative building material which has excellent heatresistance, weatherability, and abrasion resistance, provides softfeeling, and does not cause problems in the environment.

BACKGROUND ART

Heretofore, as decorative face, plates of furniture's and cabinets ofkitchen products, materials having a structure in which a decorativefilm or sheet having print of a wood pattern is laminated to a substratemade of a wood material with an adihesive have generally been used.

Decorative films and sheets used for such decorative face plates aregenerally required to have (1) workability in lapping and vacuummolding, i.e., workability which enables fitting a film or a sheet to ashape of a substrate in lamination when the substrate has an irregularshape or a complicated shape and (2) workability in V-cutting, i.e.,workability in a process comprising forming cuts of a V-shape ondecorative face plates after the plates have been assembled so thatformation of boxes or folding of end parts can be facilitated. Morespecifically, it is required that troubles, such as formation of cracks,cuts, and whitening, are not caused at folded parts of decorative filmsor sheets.

To provide decorative films and sheets with the workability in V-cuttingand lapping, films or sheets made of vinyl chloride resins haveheretofore been used. However, Vinyl chloride resins have inferiorweatherability and resistance to stains and require a large thickness tohave a sufficient strength necessary for V-cutting. Moreover, disposalof vinyl chloride resins causes a problem in that toxic chlorine gas anddioxine are formed when the resins are incinerated. Although variousproposals have been made to solve these problems, no proposals are foundto be satisfactory.

For example, a thermoplastic resin is used in place of a vinyl chlorideresin in the specification of Japanese Patent Application Laid-Open No.Heisei 3(1991)-202347. In this case, a problem arises in that a doublestructure is necessary to obtain a necessary strength, and the number ofsteps in the production process is increased. An acrylic resin is usedin the specification of Japanese Patent Application Laid-Open No. Heisei6(1994)-262729. The acrylic resin easily absorbs water, and there is thepossibility that warpage is formed in the product because of thedifference in dimensional stability. A thermosetting resin is used inthe specification of Japanese Patent Application Laid-Open No. Heisei7(1995)-244684. This resin has a drawback in that handling during theproduction is difficult. A polypropylene resin or a polyethylene resinis used in the specifications of Japanese Patent Application Laid-OpenNo. Heisei 7(1995)-17005, Japanese Patent Application Laid-Open No.Heisei 7(1995)-24979, Japanese Patent Appl ication Laid-Open No. Heisei7(1995)-137205, and Japanese Patent Application Laid-Open No. Heisei7(1995)-232415. These resins do not have a sufficient flexibility.

On the other hand, for building materials, wood and vinyl chlorideresins are mainly used. However, use of wood has a restriction becauseforests must be protected. Vinyl chloride resins have followingdrawbacks: (1) use of vinyl chloride resins causes problems becausetoxic chlorine and dioxine are formed during working and incinerationalthough the resins show excellent workability; (2) although flexibilityof vinyl chloride resins can be controlled in a wide range by usingplasticizers, plasticizers tend to bleed in molded products to causeinferior appearance; (3) floor materials made of vinyl chloride resinscannot satisfy requirements as replacements of wood because the resinshave characteristic feel of synthetic plastics in that the materials arefelt cold and rigid; and (4) vinyl chloride resins show inferior heatresistance, weatherability, and abrasion resistance.

The drawback described in (1) is particularly important for vinylchloride resins from the standpoint of protection of the environment asdescribed above for the decorative films and sheets. Therefore, vinylchloride resins are not materials suited for the global movement whichrequires materials causing no problem in the environment. Development ofmaterials which can replace vinyl chloride resins are urgently desired.

DISCLOSURE OF THE INVENTION

Under the above circumstances, the object of the present invention is toprovide a decorative film or sheet which has excellent workability inbending, V-cutting, lapping, and vacuum molding, comprises a surfacelayer having excellent transparency and hardness, and does not causeproblems in disposal so that chlorine gas is not formed by incineration,a decorative material comprising this film or sheet, and a decorativebuilding material which shows excellent heat resistance, weatherability,and abrasion resistance, has excellent property for printing andworkability in fabrication, provide,s soft feeling, and does not causeproblems in the environment.

As the result of extensive studies by the present inventors to achievethe above object, it was found that the object can be achieved by usinga film or a sheet having a laminate structure comprising a surfacelayer, an adhesive layer, and a layer having a pattern or a laminatestructure comprising a surface layer, an adhesive layer, a layer havinga pattern, an adhesive layer, and a substrate, wherein the surface layercomprises a resin mixture which comprises a specific polypropylene resinor a combination of a specific polypropylene resin and a thermoplasticelastomer copolymer in specific relative amounts. The present inventionhas been completed on the basis of this knowledge.

Accordingly, the present invention provides:

(1) A decorative film or sheet having a laminate structure comprising asurface layer, an adhesive layer, and a layer having a pattern, whereinthe surface layer is made of a film or a sheet comprising a resin whichcomprises (A) 100 to 60% by weight of a polypropylene resin comprisingone or both of a homopolymer of propylene and a copolymer of propylenecontaining 4% by weight or less of units of other olefins, thehomopolymer and the copolymer having (i) a pentad fraction expressed byrrrr/(1−mmmm)×100 of 15 to 60% as measured by a nuclear magneticresonance spectrum of an isotopic carbon (¹³C-NMR), (ii) a peaktemperature of melting (Tm) of 150° C. or higher as measured by adifferential scanning calorimeter (DSC), and (iii) an enthalpy ofmelting (ΔH) of 100 J/g or less as measured by DSC, and (B) 0 to 40% byweight of a thermoplastic elastomer copolymer;

(2) A decorative film or sheet having a laminate structure comprising asurface layer, an adhesive layer, a layer having a pattern, an adhesivelayer, and a substrate, wherein the surface layer or the surface layerand the substrate are made of a film or a sheet comprising a resin whichcomprises (A) 100 to 60% by weight of a polypropylene resin comprisingone or both of a homopolymer of propylene and a copolymer of propylenecontaining 4% by weight or less of units of other olefins, thehomopolymer and the copolymer having (i) a pentad fraction expressed byrrrr/(1−mmmm)×100 of 15 to 60% as measured by a nuclear magneticresonance spectrum of an isotopic carton (¹³C-NMR), (ii) a peaktemperature of melting (Tm) of 150° C. or higher as measured by adifferential scanning calorimeter (DSC), and (iii) an enthalpy ofmelting (ΔH) of 100 J/g or less as measured by DSC, and (B) 0 to 40% byweight of a thermoplastic elastomer copolymer;

(3) A decorative material comprising the decorative film or sheetdescribed in (1) which is bonded to a substrate selected from woodsubstrates, metal substrates, inorganic substrates, and resinsubstrates;

(4) A decorative material comprising the decorative film or sheetdescribed in (2) which is bonded to a substrate selected from woodsubstrates, metal substrates, inorganic substrates, and resinsubstrates; and

(5) A decorative building material having a surface layer comprising aresin which comprises (A) 100 to 60% by weight of a polypropylene resincomprising one or both of a homopolymer of propylene and a copolymer ofpropylene containing 4% by weight or less of units of other olefins, thehomopolymer and the copolymer having (i) a pentad fraction expressed byrrrr/(1−mmmm)×100 of 15 to 60% as measured by a nuclear magneticresonance spectrum of an isotopic carbon (¹³C-NMR), (ii) a peaktemperature of melting (Tm) of 150° C. or higher as measured by adifferential scanning calorimeter (DSC), and (iii) an enthalpy ofmelting (ΔH) of 100 J/g or less as measured by DSC, and (B) 0 to 40% byweight of a thermoplastic elastomer copolymer.

THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION

The decorative film or sheet of the present invention has a laminatestructure comprising a surface layer, an adhesive layer, and a layerhaving a pattern or a laminate structure comprising a surface layer, anadhesive layer, a layer having a pattern, an adhesive layer, and asubstrate. In the present invention, a film or a sheet comprising apolypropylene resin of component (A) which comprises one or both of ahomopolymer of propylene and a copolymer of propylene containing 4% byweight or less of units of other olefins and has specific structures andproperties described below or a resin mixture containing component (A)and a thermoplastic elastomer copolymer of component (B) is used as asurface layer or a surface layer and a substrate comprised in thedecorative film or sheet.

The specific structures and properties of the homopolymer and thecopolymer of propylene described above are described in the following in[i] to [iii].

(i) Firstly, it is necessary that the pentad fraction expressed byrrrr/(1−mmmm)×100 be in the range of 15 to 60% as measured by a nuclearmagnetic resonance spectrum of an isotopic carbon (¹³C-NMR). When thisvalue is less than 15%, heat resistance is insufficient. When this valueexceeds 60%, flexibility is insufficient, and workability in V-cuttingand lapping becomes inferior. The value of rrrr/(1−mmmm)×100 ispreferably in the range of 15 to 50%, more preferably in the range of 20to 40%, from the standpoint of the balance between heat resistance andflexibility. In this description, rrrr means a configuration in whichfive methyl groups attached to a main chain formed by carbon-carbonbonds of arbitrarily selected five successive propylene units aredisposed at alternately opposite relative positions or a fraction ofthis configuration, and mmmm means a configuration in which five methylgroups attached to a main chain formed by carbon-carbon bonds arearbitrarily selected five successive propylene units are disposed at thesame relative positions or a fraction of this configuration.

The value of rrrr/(1−mmmm) is measured in accordance with the followingmethod. Measurement of 13C-NMR is conducted using JNM-FX-200(manufactured by NIPPON DENSHI Co., Ltd.; resonance frequency of the ¹³Cnucleus, 50.1 MHz) at the following mode of measurement: completedecoupling of proton; pulse width, 6.9 μs (45°); repeating time ofpulse, 3 s; number of accumulation, 10,000; solvent,1,2,4-trichlorobenzene/heavy benzene (90/10% by volume); concentrationof sample, 250 mg/2.5 ml of solvent; and temperature of the measurement,130° C. The fractions of pentads are measured using difference in thechemical shift depending on the stereoregularity of methyl group.Specifically, the pentad fractions are obtained from ratios ofintensities by area between the following peaks of mmmm to mrrm whichare observed in the region of 22.5 to 19.5 ppm, and the value ofrrrr/(1−mmmm)×100 was obtained from these pentad fractions.

mmmm: 21.86 ppm mmmr: 21.62 ppm mmrr: 21.08 ppm mmrm + rrmr: 20.89 ppmrrrr: 20.36 ppm mrrm: 19.97 ppm

[ii] Secondly, it is necessary that the peak temperature of melting (Tm)be 150° C. or higher as measured by a differential scanning calorimeter(DSC). When Tm is lower than 150° C., sufficient heat resistance cannotbe obtained.

Tm is generally in the range of 150 to 165° C. Measurement of Tm isconducted using DSC-7 manufactured by PERKIN-ELMER Company, and thevalue of Tm is obtained as lthe peak temperature of melting inaccordance with the method of Japanese Industrial Standard K-7121.

[iii] Thirdly, it is necessary that the enthalpy of melting (ΔH) be 100J/g or less as measured by DSC. When ΔH exceeds 100 J/g, flexibilitydeteriorates, and workability in V-cutting and lapping becomes inferior.ΔH is preferably in the range of 10 to 100 J/g because strength isinsufficient when ΔH is excessively small. Measurement of ΔH isconducted using DSC-7 manufactured by PERKIN-ELMER Company, and ΔH isobtained as the total heat energy absorbed during melting of crystals inaccordance with the method of Japanese Industrial Standard K-7122. Themeasurement using DSC is conducted at the following measurement mode:sample is held at 230° C. for 3 minutes; then, temperature is decreasedto 50° C. at a speed of 10° C./minute; sample is held at 50° C. for 3minutes; and then, temperature is increased to 230° C. at a speed of 10°C./minute.

It is preferable that the above homopolymer of propylene and thecopolymer of propylene containing 4% by weight or less of units of otherolefins contain a fraction soluble in boiling n-heptane in the range of7 to 50% by weight. When the content of the fraction soluble in boilingn-heptane is less than 7% by weight, flexibility is insufficient, andthere is the possibility that workability in V-cutting and lappingbecomes inferior. When the content of the fraction soluble in boilingn-heptane exceeds 50% by weight, sufficient mechanical strengths andheat resistance cannot be obtained. The content of the fraction solublein boiling n-heptane is more preferably in the range of 10 to 40% byweight from the standpoint of the balance between flexibility,mechanical strengths, and heat resistance. The content of the fractionsoluble in boiling n-heptane is obtained by extraction of a sample withboiling n-heptane for 6 hours using a Soxhlet extractor and thencalculating the dissolved amount from the extracted amount.

On the other hand, in the decorative building material of the presentinvention, a polypropylene resin of component (A′) comprising one orboth of a homopolymer of propylene and a copolymer of propylenecontaining 4% by weight or less of units of other olefins and havingspecific structures and properties described below or a resin mixturecontaining component (A′) and a thermoplastic elastomer copolymer ofcomponent (B) is used as a surface layer.

The specific structures and properties of the homopolymer and thecopolymer of propylene described above are described in the following in[i] to [iii].

(i) Firstly, the pentad fraction expressed by rrrr/1-mmmm)×100 is in therange of 15 to 60% as measured by a nuclear magnetic resonance spectrumof an isotopic carbon (¹³C-NMR). When this value is less than 15%, heatresistance is insufficient. When this value exceeds 60%, flexibility isinsufficient. The value of rrrr/1−mmmm×100 is preferably in the range of20 to 60%, more preferably in the range of 25 to 55%, from thestandpoint of the balance between heat resistance and flexibility.

[ii] Secondly, the peak temperature of melting (Tm) is 150° C. or higheras measured by a differential scanning calorimeter (DSC). When Tm islower than 150° C., sufficient heat resistance cannot be obtained. Tm isgenerally in the range of 150 to 165° C.

[iii] Thirdly, the enthalpy of melting (ΔH) is 100 J/g or less asmeasured by DSC. When ΔH exceeds 100 J/g, flexibility deteriorates, andthe object of the present invention cannot be achieved. ΔH is preferablyin the range of 10 to 100 J/g, more preferably in the range of 20 to 100J/g, most preferably 40 to 90 J/g, because strength is insufficient whenΔH is excessively small.

The homopolymer of propylene and the copolymer of propylene containing4% by weight or less of units of other olefins preferably have afraction soluble in boiling n-heptane in the range of 7 to 50% byweight. When the content of the fraction soluble in boiling n-heptane isless than 7% by weight, there is the possibility that flexibility isinferior. When the content of the fraction soluble in boiling n-heptaneexceeds 50% by weight, there is the tendency that sufficient mechanicalstrengths and heat resistance cannot be obtained. The content of thefraction soluble in boiling n-heptane is more preferably in the range of10 to 40% by weight from the standpoint of the balance betweenflexibility, mechanical strengths, and heat resistance.

The methods of measurement of the fraction of pentad, the peaktemperature of melting (Tm), the enthalpy of melting (ΔH), and thefraction soluble in boiling n-heptane in component (A′) are the same asthe methods used for measurement of the corresponding properties ofcomponent (A) in the above decorative film or sheet.

In the homopolymer of propylene and the copolymer containing 4% byweight or less of units of other olefins in component (A) and component(A′) described above, it does not generally occur in the sequence of theunits of propylene that carbon atoms having methyl group as the sidegroup are placed next to each other and bonded directly to each other.In other words, reversed bonding of monomer units does not occur, andcarbon atoms having methyl group as the side group are regularlyarranged with another carbon atom between them. In still other words, inthe present invention, units of propylene are bonded to each other inthe heat-to-tail bonding, and the head-to-head bonding and thetail-to-tail bonding are substantially absent.

Examples of the olefins as the comonomer forming the units of otherolefins in the copolymer of propylene containing 4% by weight or less ofunits of other olefins include α-olefins, such as ethylene, butene-1,pentene-1, 4-methyl-1-pentene, hexene-1, heptene-1, octene-1, nonene-1,and decene-1. Among these olefins, ethylene is preferable. The olefincan be used singly or as a combination of two or more types. It isnecessary that the olefin used as the comonomer be used in such anamount that the content of the unit derived from the olefin in thecopolymer of propylene is 4% by weight or less.

In the present invention, the polypropylene resin used as component (A)or component (A′) preferably has a melt index (MI) in the range of 0.1to 50 g/10 minutes. When MI is less than 0.1 g/10 minutes, moldingbecomes difficult. When MI exceeds 50 g/10 minutes, mechanicalproperties of the obtained films, sheets, and molded products areinsufficient. From the standpoint of the balance between moldability andmechanical properties of obtained films, sheets, and molded products, MIis more preferably in the range of 0.2 to 30 g/10 minutes. MI is thevalue obtained in accordance with the method of Japanese IndustrialStandard K7210 at a load of 2.16 kgf and a temperature of 230° C.

The polypropylene resin used as component (A) and component (A′) in thepresent invention can be produced, for example, in accordance with thesingle step gas phase polymerization process, the single step slurrypolymerization process, the multi-step gas phase polymerization process,the multi-step slurry polymerization process, or the blending process.For example, when the polypropylene resin is produced in accordance withone of the above polymerization processes, propylene can behomopolymerized or copolymerized with other olefins in the presence of acatalyst system comprising:

(a) a solid component constituted with (i) a solid catalyst componentcomprising magnesium, titanium, a halogen atom, and an electron donorand, optionally, (ii) a crystalline polyolefin;

(b) an organoaluminum compound;

(c) an aromatic compound containing alkoxy groups which is representedby general formula (I):

wherein R¹ represents an alkyl group having 1 to 20 carbon atoms, R²represents a hydrocarbon group having 1 to 10 carbon atoms, hydroxylgroup, or nitro group, m represents an integer of 1 to 6, and nrepresents an integer of 0 to (6-m); and optionally,

(d) an electron donating compound.

The above solid component of component (a) is constituted with a solidcatalyst component comprising magnesium, titanium, a halogen atom, andan electron donor of component (i) and, optionally, a crystallinepolyolefin of component (ii). The solid catalyst component of component(i) contains magnesium titanium, a halogen atom, and an electron donoras the essential components and can be prepared by bringing a magnesiumcompound and a titanium compound into contact with an electron donor.The halogen atom is contained in the magnesium compound or the titaniumcompound in the form of a halide.

Examples of the magnesium compound include magnesium dihalides, such asmagnesium dichloride; magnesium oxide; magnesium hydroxide;hydrotalcite; magnesium salts of carboxylic acids; dialkoxymagnesiums,such as dialkoxymagnesium; diaryloxymagnesiums; alkoxymagnesium halides;aryloxymagnesium halides; dialkylmagnesiums, such asethylbutylmagnesium; and reaction products of organomagnesium compoundswith electron donors, halosilanes, alkoxysilanes, silanols, and aluminumcompounds. Among these compounds, magnesium dihalides,dialkoxymagnesiums, and alkylmagnesium halides are preferable. Themagnesium compound can be used singly or as a combination of two or moretypes.

Reaction products of magnesium metal and a halogen and reaction productsof magnesium metal, compounds containing a halogen, and alcohols canalso be used as the magnesium compound. The magnesium metal is notparticularly limited, and magnesium metal having any grain size, such asmagnesium metal in the form of granules, ribbons, and powder, may beused. The surface condition of magnesium metal is not particularlylimited, either. However, it is preferable that magnesium metal is notcoated with a film, such as a film of magnesium oxide.

As the alcohol, any alcohol may be used. Lower alcohols having 1 to 6carbon atoms are preferable, and ethanol is more preferable because asolid catalyst component providing remarkably enhanced performances tothe catalyst can be obtained. The purity of the alcohol or the contentof water in the alcohol are not particularly limited. However, it ispreferable that an alcohol containing water in an amount of 1% by weightor less, more preferably 2,000 ppm or less, is used because magnesiumhydroxide is formed on the surface of magnesium metal when an alcoholcontaining a large amount of water is used. The smaller the content ofwater, the more advantageous the alcohol.

The type of the halogen or the compound containing a halogen is notparticularly limited. Any compound containing a halogen atom in themolecule can be used as the compound containing a halogen. In such acompound, the type of the halogen atom is not particularly limited.Chlorine, bromine, and iodine are preferable, and iodine is morepreferable. Among the compounds containing a halogen atom, metalcompounds containing a halogen are particularly preferable. The form,the shape, and the size of the grain of these compounds are notparticularly limited, and any form shape, and size can be used. Forexample, a solution in an alcoholic solvent, such as ethanol, can beused.

The amount of the alcohol is selected generally in the range of 2 to 100mol, preferably in the range of 5 to 50 mol, per 1 mol of magnesiummetal. When the amount of the alcohol exceeds the above range, there isthe tendency that a magnesium compound having an advantageous morphologyis not obtained. When the amount of the alcohol is less than the aboverange, there is the possibility that the reaction with magnesium metaldoes not proceed :smoothly.

The halogen or the compound containing a halogen is generally used insuch an amount that the halogen atom is contained in the range of 0.0001g atom or more, preferably in the range of 0.0005 g atom or more, morepreferably in the range of 0.001 g atom or more, per 1 g atom ofmagnesium metal. When the amount of the halogen atom is less than 0.0001g atom, the use of the magnesium compound without pulverization causesinferior supporting amount, activity, and stereoregularity andmorphology of the produced polymer, and the treatment of the magnesiumcompound by pulverization is indispensable. Therefore, such an amount isnot preferable. It is possible that the grain size of the obtainedmagnesium compound is controlled to a desired value by suitablyselecting the amount of the halogen or the compound containing halogen.

The reaction of magnesium metal, an alcohol, and a halogen or a compoundcontaining a halogen can be conducted in accordance with a conventionalprocess. For example, in a conventional process, magnesium metal, analcohol, and a halogen or a compound containing a halogen are broughtinto reaction with each other under the refluxing condition untilgeneration of hydrogen is not observed any more, generally for about 20to 30 hours, to obtain the desired magnesium compound. Morespecifically, when iodine is used as the halogen, for example, magnesiummetal and solid iodine are thrown into an alcohol, and the mixture isrefluxed by heating. In another process, an alcohol solution of iodineis added dropwise to the alcohol containing magnesium metal, and thenthe alcohol solution is refluxed by heating. In still another process,an alcohol solution of iodine is added dropwise into an alcohol solutioncontaining magnesium metal with heating. In any of these processes, itis preferable that the reaction is conducted in an atmosphere of aninert gas, such as nitrogen gas and argon gas, and where desired, in aninert organic solvent, such as a saturated hydrocarbon such as n-hexane.As for the addition of magnesium metal, an alcohol, and a halogen or acompound containing a halogen, it is not necessary that the entireamount of these materials are placed in the reactor at the beginning ofthe reaction, and these materials can be added in separate portions. Itis particularly preferable that the entire amount of an alcohol isplaced into the reactor at the beginning of the reaction, and magnesiummetal is added to the reactor in several separate portions.

The above process is very preferable from the standpoint of safetybecause formation of a large amount of hydrogen gas in a short time canbe prevented. Decrease in the size of the reactor is also possible.Moreover, removal of the alcohol and the halogen or the compoundcontaining a halogen accompanied with droplets of the reaction solutionformed by generation of a large amount of hydrogen gas in a short timecan be prevented. The number of the separate addition can be decided inaccordance with the scale of the reactor, and it is generally preferablethat the number of the addition is 5 to 10 when more complicatedoperations caused by an increased number of the addition is considered.Of course, any of a batch process and a continuous process can be used.A process, in which a small portion of magnesium metal is added to theentire amount of an alcohol, the product formed by the reaction isseparated and removed into another tank, another small portion ofmagnesium metal is added to the remaining reaction mixture, and theseprocedures are repeated, may be adopted as a modified process.

Before the magnesium compound thus obtained is used for the preparationof the solid catalyst component, the magnesium compound may be dried orwashed with an inert solvent, such as n-heptane, after filtration. Inany cases, the obtained magnesium compound can be used in the next stepwithout pulverization or classification for adjustment of distributionof the grain size.

Examples of the titanium compound include tetraalkoxytitaniums, such asitetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium,tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium,tetracyclohexyloxytitanium, and tetraphenoxytitanium; titaniumtetrahalides, such as titanium tetrachloride, titanium tetrabromide, andtitanium tetraiodide; monoalkoxytitanium trihalides, such asmethoxytitanium trichloride, ethoxytitanium trichloride,propopxytitanium trichloride, n-butoxytitanium trichloride, andethoxytitanium tribromide; dialkoxytitanium dihalides, such asdimethoxytitanium dichloride, diethoxytitanium dichloride,dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, anddiethoxytitanium dibromide; and trialkoxytitanium monohalides, such astrimethoxytitanium chloride, triethoxytitanium chloride,tripropoxytitanium chloride, and tri-n-butoxytitanium chloride. Amongthese titanium compounds, titanium compounds containing a larger numberof a halogen are preferable, and titanium tetrachloride is morepreferable. The titanium compound can be used singly or as a combinationof two or more types.

As the electron donor, compounds shown later as examples of the electrondonating compounds of component (d) can be used.

The preparation of the solid catalyst component of component (i) can beconducted in accordance with conventional processes described in thespecifications of Japanese Patent Application Laid-Open No. Showa53(1978)43094, Japanese Patent Application Laid-Open No. Showa55(1980)-135102, Japanese Patent Application Laid-Open No. Showa55(1980)-135103, Japanese Patent Application Laid-Open No. Showa56(1981)-18606, Japanese Patent Application Laid-Open No. Showa56(1981)-166205, Japanese Patent Application Laid-Open No. Showa57(1982)-63309, Japanese Patent Application Laid-Open No. Showa57(1982)-190004, Japanese Patent Application Laid-Open No. Showa57(1982)-300407, and Japanese Patent Application Laid-Open No. Showa58(1983)47003.

The solid catalyst component of component (i) thus prepared generallyhas the following composition: the ratio by atom of magnesium totitanium, in the range of 2 to 100; the ratio by atom of the halogen totitanium, in the range of 5 to 100; and the ratio by mol of the electrondonor to titanium, in the range of 0.1 to 10.

Examples of the crystalline polyolefin of component (ii) which isoptionally used in the preparation of the solid component of component(a) include crystalline polyolefins obtained from α-olefins having 2 to10 carbon atoms, such as polyethylene, polypropylene, polybutene, andpoly-4-methyl-1-pentene. The crystalline polyolefin can be obtained inaccordance with (1) a process in which an olefin is preliminarilypolymerized in the presence of a combination of the solid catalystcomponent of component (i) described above, an organoaluminum compound,and the optionally used electron donating compound (a process ofpreliminary polymerization), (2) a process in which the solid catalystcomponent of component (i) described above and an organoaluminumcompound and the electron donating compound (having a melting point of100° C. or higher) which are used optionally are dispersed incrystalline powder, such as crystalline polyethylene and polypropylene,having a uniform particle size (a dispersion process), or (3) a combinedprocess of process (1) and process (2) described above.

In the process of the process of preliminary polymerization of process(1), the ratio by atom of aluminum to titanium is generally selected inthe range of 0.1 to 100, preferably in the range of 0.5 to 50, and theratio by mol of the electron donating compound to titanium is generallyselected in the range of 0 to 50, preferably in the range of 0.1 to 20.

The relative amounts of the solid catalyst component of component (i) tothe crystalline polyolefin of component (ii) in the solid component ofcomponent (a) are selected so that the ratio by weight of component (i)to component (ii) is generally in the range of 0.33 to 200, preferably0.10 to 50.

Examples of the organoaluminum compound used as component (b) includecompounds represented by general formula (I):

AlR³ _(p)X_(3−p)  (II)

wherein R³ represents an alkyl group having 3 to 20 carbon atoms or anaryl group having 6 to 20 carbon atoms, X represents a halogen atom, andp represents a number of 1 to 3. Preferable examples of theorganoaluminum compound include trialkylaluminums, such astriisopropylaluminum, triisobutylaluminum, and trioctylaluminum; anddialkylaluminum monohalides, such as diethylaluminum monochloride,diisopropylaluminum monochloride, diisobutylaluminum monochloride, anddioctylaluminum monochloride, and alkylaluminum sesquihalides, such asethylaluminum sesquichloride. The organoaluminum compound can be usedsingly or as a combination of two or more types.

The catalyst system used in the present invention comprises, ascomponent (c), an aromatic compound containing alkoxy groups which isrepresented by general formula (I):

wherein R¹ represents an alkyl group having 1 to 20 carbon atoms, R²represents a hydrocarbon group having 1 to 10 carbon atoms, hydroxylgroup, or nitro group, m represents an integer of 1 to 6, and nrepresents an integer of 0 to (6-m).

Specific examples of the aromatic compound containing alkoxy groupsinclude monoalkoxy compounds, such as m-methoxytoluene, o-methoxyphenol,m-methoxyphenol, 2-methoxy-4-methylphenol, vinylanisole,p-(1-propenyl)anisole p-allylanisole,1,3-bis(p-methoxy-phenyl)-1-pentene, 5-allyl-2-methoxyphenol,4-hydroxy-3-methoxybenzyl alcohol, methoxybenzyl alcohol, nitroanisole,and nitrophenetole; dialkoxy compounds, such as o-dimethoxybenzenem-dimethoxybenzene, p-dimethoxybenzene, 3,4-dimethoxytoluene,2,6-dimethoxyphenol, and 1-allyl-3,4-dimethoxybenzene; and trialkoxycompounds, such as 1,3,5-trimethoxybenzene,5-allyl-1,2,3-trimethoxybenzene, 5-allyl-1,2,4-trimethoxybenzene,1,2,3-trimethoxy-5-(1-propenyl)benzene,1,2,4-trimethoxy-5-(1-propenyl)benzene, 1,2,3-trimethoxybenzene, and1,2,4-trimethoxybenzene. Among these compounds, dialkoxy compounds andtrialkoxy compounds are preferable. The aromatic compound containingalkoxy groups can be used singly or as a combination of two or moretypes.

An electron donating compound is used as component (d) in the catalyst,where necessary. The electron donating compound is a compound containingoxygen, nitrogen, phosphorus, sulfur, or silicon and essentially acompound having the ability to increase the regularity in thepolymerization of propylene.

Examples of the electron donating compound include organosiliconcompounds, esters, thioesters, amines, ketones, nitrites, phosphines,ethers, thioethers, acid anhydrides, acid halides, acid amides,aldehydes, organic acids, and azo compounds.

Specific examples of the electron donating compound includeorganosilicon compounds, such as diphenyldimethoxysilane,diphenyldiethoxysilane, dibenzyldimethoxysilane, tetramethoxysilane,tetraethoxysilane, tetraphenoxysilane, methyltrimethoxysilane,methyltriethoxysilane, methyltriphenoxysilane, phenyltrimethoxysilane,phenyltriethoxysilane, benzyltrimethoxysilane, andcyclohexylmethyldimethoxysilane; esters of aromatic dicarboxylic acid,such as monomethyl phthalate, monoethyl phthalate, monopropyl phthalate,monobutyl phthalate, monoisobutyl phthalate, monoamyl phthalate,monoisoamyl phthalate, monomethyl terephthalate, monoethylterephthalate, monopropyl terephthalate, monobutyl terephthalate,monoisobutyl terephthalate, dimethyl phthalate, diethyl phthalate,dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamylphthalate, diisoamyl phthalate, methyl ethyl phthalate, methyl isobutylphthalate, methyl propyl phthalate, ethyl butyl phthalate, ethylisobutyl phthalate, ethyl propyl phthalate, propyl isobutyl phthalate,dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate,diisobutyl terephthalate, methyl ethyl terephthalate, methyl isobutylterephthalate, methyl propyl terephthalate, ethyl butyl terephthalate,ethyl isobutyl terephthalate, ethyl propyl terephthalate, propylisobutyl terephthalate, dimethyl isophthalate, diethyl isophthalate,dipropyl isophthalate, diisobutyl isophthalate, methyl ethylisophthalate, methyl isobutyl isophthalate, methyl ethyl isophthalate,methyl isobutyl isophthalate, methyl propyl isophthalate, ethyl butylisophthalate, ethyl isobutyl isophthalate, ethyl propyl isophthalate,and propyl isobutyl isophthalate; monoesters, such as methyl formate,ethyl formate, methyl acetate, ethyl acetate, vinyl acetate, propylacetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methylbutyrate, ethyl butyrate, ethyl valerate, methyl chloroacetate, ethyldichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate,dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethylbenzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexylbenzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyltoluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethylanisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethylo-chiorobenzoate, and ethyl naphthoate; esters, such as γ-butyrolactone,δ-valerolactone, coumarine, phthalide, and ethylene carbonate; organicacids, such as benzoic acid and p-oxybenzoic acid; acid anhydrides, suchas succinic anhydride, benzoic anhydride, and p-toluic anhydride;ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone,acetophenone, benzophenone, and benzoquinone; aldehydes, such asacetaldehyde, propionaldehyde, octylaldehyde, tolualdehyde,benzaldehyde, and naphthylaldehyde; acid halides, such as acetylchloride, acetyl bromide, propionyl chloride, butyryl chloride,isobutyryl chloride, 2-methylpropionyl chloride, valeryl chloride,isovaleryl chloride, hexanoyl chloride, methylhexanoyl chloride,2-ethylhexanoyl chloride, octanoyl chloride, decanoyl chloride,undecanoyl chloride, hexadecanoyl chloride, octadecanoyl chloride,benzylcarbonyl chloride, cyclohexanecarbonyl chloride, malonyldichloride, succinyl dichloride, pentanedioleyl dichloride,hexanedioleyl dichloride, cyclohexanedicarbonyl dichloride, benzoylchloride, benzoyl bromide, methylbenzoyl chloride, phthaloyl chloride,isophthaloyl chloride, terephthaloyl chloride, andbenzene-1,2,4-tricarbonyl trichloride; ethers, such as methyl ether,ethyl ether, isopropyl ether, n-butyl ether, isopropyl methyl ether,isopropyl ethyl ether, t-butyl ethyl ether, t-butyl n-propyl ether,t-butyl n-butyl ether, t-amyl methyl ether, t-amyl ethyl ether, amylether, tetrahydrofuran, anisole, diphenyl ether, and ethylene glycolbutyl ether; acid amides, such as acetamide, benzamide, and toluamide;amines, such as tributylamine, N,N′-dimethylpiperadine, tribenzylamine,aniline, pyridine, pyrroline, and tetramethylethylenediamine; nitrites,such as acetonitrile, benzonitrile, and tolunitrile; and azo compound shaving sterically hindered groups bonded to the azo linkage, such ads2,2′-azobis(2-methylpropane), 2,2′-azobis(2-ethylpropane), and2,2′-azobis(2-methylpentane).

Among these compounds, organosilicon compounds, esters, ketones, ethers,thioethers, acid anhydrides, and acid halides are preferable. Morepreferable examples include organosilicon compounds, such asdiphenyldimethoxysilane, phenyltriethoxysilane, andcyclohexylmethyldimethoxysilane; and diesters of aromatic dicarboxylicacids, such as di-n-butyl phthalate and diisobutyl phthalate; alkylesters of aromatic monocarboxylic acids, such as benzoic acid,p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluic acid. Theelectron donating compound can be used singly or as a combination of twoor more types.

As for the amounts of the components used in the catalyst, the solidcomponent of component (a) is generally used in such an amount that theamount of titanium atom is in the range of 0.0005 to 1 mol per 1 literof the reaction volume. The organoaluminum compound of component (b) isused in such an amount that the ratio by atom of aluminum to titanium isgenerally 1 to 3,000, preferably 40 to 800. When this amount is outsidethe above range, there is the possibility that the catalyst activity isinsufficient. The aromatic compound containing alkoxy groups ofcomponent (c) is used in such an amount that the ratio by mol of thecompound containing alkoxy groups to titanium atom in the solidcomponent of component (a) is generally 0.01 to 500, preferably 1 to300. When this ratio is less than 0.01, there is the possibility thatphysical properties of the formed polymer are inferior. When this ratioexceeds 500, there is the possibility that the catalyst activity isinsufficient.

In the present invention, the polypropylene resin of component (A) andcomponent (A′) can be produced by homopolymerization of propylene orcopolymerization of propylene with small amounts of other olefins in thepresence of the above catalyst, for example, in accordance with a singlestage polymerization.

The process of the polymerization is not particularly limited, and theslurry polymerization process, the gas phase polymerization process, thebulk polymerization process, the solution polymerization process, or thesuspension polymerization process can be used.

When the polymerization is conducted in accordance with the gas phasepolymerization process, the polymerization pressure is suitably selectedgenerally in the range of 10 to 45 kg/cm², preferably in the range of 20to 30 kg/cm², and the polymerization temperature is suitably selectedgenerally in the range of 40 to 90° C., preferably in the range of 60 to75° C. The molecular weight of the polymer can be controlled inaccordance with a conventional method, such as control of theconcentration of hydrogen in the polymerization reactor. The molecularweight of the polymer can also be adjusted by producing a (co)polymerhaving a relatively high molecular weight in the polymerization stage,followed by melt kneading the obtained (co)polymer in the presence of anorganic peroxide. The polymerization time is suitably selected in therange of about 5 minutes to 10 hours.

To carry out the polymerization, the components constituting thecatalyst system, i.e., components (a) to (d), are mixed together in thespecified relative amounts to bring the components in contact with eachother. Immediately after the catalyst components are mixed together, themonomer may be introduced, and the polymerization is allowed to start.Alternatively, the catalyst system may be aged for about 0.2 to 3 hoursafter the catalyst components are mixed together, and subsequently themonomer is introduced. The catalyst components may be supplied in theform of a suspension in an inert solvent or the olefin used as thematerial monomer.

The polymer obtained after the polymerization can be treated inaccordance with a conventional method. In the gas polymerizationprocess, a stream of nitrogen gas may be passed through powder of thepolymer discharged from the polymerization reactor after thepolymerization to remove unreacted monomer. Alternatively, the polymerdischarged from the polymerization reactor may be pelletized using anextruder, where desired. A small amount of water or alcohol may be addedto completely deactivate the catalyst. In the bulk polymerizationprocess, the polymer, discharged from the polymerization reactor may bepelletized after the unreacted monomer has been removed completely.

The polypropylene resin of component (A) and component (A′) thusobtained has properties more advantageous than those of conventionalpolyolefin thermoplastic elastomers. The present polymer has moreexcellent resistance to whitening, transparency, and surface hardness.The present polymer shows more excellent workability in vacuum molding,for example, tighter attachment of a film or a sheet to a substrate inthe vacuum molding. Moreover, a surface layer can be formed using a filmor a sheet having a single layer.

The polypropylene resin of component (A) and component (A′) can be usedsingly or as a mixture with thermoplastic elastomer copolymers as shownin the following.

In the decorative film or sheet of the present invention, the abovepolypropylene resin of component (A) or a resin mixture comprising thepolypropylene resin of component (A) and a thermoplastic elastomer ofcomponent (B) may be used for the film or the sheet of a surface layeror a surface layer and a substrate.

In the decorative building material of the present invention, the abovepolypropylene resin of component (A′) or a resin mixture comprising thepolypropylene resin of component (A′) and a thermoplastic elastomer ofcomponent (B) may be used for the film or the sheet of a surface layer.

The thermoplastic elastomer used as component (B) is a copolymer whichshows the properties required for a thermoplastic resin, i.e.,plasticity and fluidity, at a temperature of molding and rubberyproperties at an ambient temperature before or after the molding.

Examples of the thermoplastic elastomer include elastomers of copolymersof styrene and a diene; hydrogenation products of these copolymers;elastomers of copolymers of ethylene and an α-olefin having 3 or morecarbon atoms; elastomers of copolymers of ethylene, α-olefin having 3 ormore carbon atoms, and a polyene; hydrogenation products of thesecopolymers; elastomers of copolymers of ethylene, an unsaturatedcarboxylic acid, and an ester of an α,β-unsaturated carboxylic acid; andelastomers of copolymers of acrylonitrile.

Examples of the copolymer of styrene and a diene include blockcopolymers of aromatic vinyl compounds, such as styrene,α-methylstyrene, and vinyltoluene, and conjugated dienes, such asbutadiene and isoprene. As the aromatic vinyl compound, styrene isparticularly preferable. The block copolymer may be a single blockcopolymer, a tereblock copolymer, a radial tereblock copolymer, or amultiblock copolymer.

The amount of the aromatic vinyl compound in the copolymer of styreneand a diene is preferably in the range of 10 to 50% by weight. When theamount is less than 10% by weight, moldability of the obtained resinmixture tends to be inferior. When the amount exceeds 50% by weight,impact resistance at a low temperature tends to be inferior.

When the units of a conjugated diene in the above block copolymer arehydrogenated, heat resistance can be improved by the increased amount ofunsaturation in the main chain. Copolymers having the blocks ofstyrene-ethylene-butylene-styrene are particularly preferable.

Examples of the above copolymer of ethylene and α-olefins having 3 ormore carbon atoms include copolymers of ethylene with propylene,butene-1, hexene-1, or octene-1. The copolymer may be {i} a copolymerobtained in accordance with a two-stage copolymerization in the presenceof component (A) or component (A′), or {ii} a copolymer obtained bycopolymerization in the absence of component (A) or component (A′). Inthe case of copolymer {i}, the copolymer contains about 10 to 80% byweight of the unit. of ethylene. A copolymer of ethylene and propylenecontaining 20 to 70% by weight of the unit of ethylene is a typicalexample. In the case of copolymer (ii), the copolymer contains generallyabout 20 to 90% by weight, preferably 30 to 85% by weight, of the unitof ethylene.

In the elastomer of a copolymer of ethylene, α-olefin having 3 or morecarbon atoms, and a polyene, for example, one or more compounds selectedfrom propylene, butene-1, hexene-1, heptene-1, octene-1, nonene-1,decene-1, undecene-1, and dodecene-1 is used as the α-olefin having 3 ormore carbon atoms. As the polyene, one or more compounds selected fromconjugated dienes, such as butadiene, isoprene, and piperylene;non-conjugated dienes, such as 1,4-hexadiene, 1,6-octadiene,2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene,cyclohexadiene, dicylcopentadiene, methyltetrahydroindene,5-ethylidene-2-norbornene, 5-methylene-2-norbornene,5-isopropylidene-2-norbornene, and6-chloromethyl-5-isopropenyl-2-norbornene; and trienes, such as2,3-diisopropylidene-5-norbornene,2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornene,1,3,7-octatriene, and 1,4,9-decatriene can be used. Among thesecompounds, diene compounds, such as conjugated dienes and non-conjugateddienes, are preferable. To effectively exhibit the properties as anelastomer, it is preferable that the c6ntent of the polyene in thecopolymer is adjusted so that the copolymer has an iodine value of 30 orless, more preferably in the range of 5 to 25. The copolymer may behydrogenated to adjust the iodine value within the above range.

In the elastomer of a copolymer of ethylene, an unsaturated carboxylicacid, and ester of an α,β-unsaturated carboxylic acid, examples of theα,β-unsaturated carboxylic acid include acrylic acid, methacrylic acid,ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonicacid, isocrotonic acid, citraconic acid, sorbic acid, mesaconic acid,and angelic acid. These compound can be used singly or as a combinationof two or more types.

Examples of the ester of the α,β-ethylenically unsaturated carboxylicacid include esters of α,β-ethylenically unsaturated carboxylic acidspreferably having 3 to 8 carbon atoms, such as acrylic acid, methacrylicacid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid,crotonic acid, and isocrotonic acid, and monohydric alcohols, such asmethyl alcohol, ethyl alcohol, isopropyl alcohol, and n-propyl alcohol,dihydric alcohols, such as ethylene glycol and propylene glycol, orpolyhydric alcohols, such as glycerol and pentaerythritol. The ester canbe used singly or as a combination of two or more types.

As the above copolymers, copolymers containing derivatives of the aboveunsaturated carboxylic acids, such as acid anhydrides, amides, imides,and metal salts, can also be used, where desired.

It is preferable that the above copolymer contains 50 to 95% by weightof the unit of ethylene, 1 to 10% by weight of the unit of theunsaturated carboxylic acid, and 4 to 49% by weight of the unit of theester of the α,β-ethylenically unsaturated carboxylic acid in randomsequences and exhibits the properties as an elastomer.

When the content of the unit of ethylene exceeds 95% by weight or thecontent of the unit of the ester of the α,β-ethylenically unsaturatedcarboxylic acid is less than 4% by we ight, there is the possibilitythat the properties as an elastomer are not sufficiently exhibited. Whenthe content of the unit of ethylene is less than 50% by weight or thecontent of the unit of the ester of the α,β-ethyienically unsaturatedcarboxylic acid exceeds 49% by weight, impact resistance at a lowtemperature tends to become inferior. When the content of the unit ofthe unsaturated carboxylic acid is less than 1% by weight, thecrosslinking property is inferior. When the content of the unit of theunsaturated carboxylic acid exceeds 10% by weight, the properties as anelastomer are not sufficient.

Examples of the elastomer of a copolymer of acrylonitrile includecopolymers of unsaturated nitriles, such as acrylonitril andmethacrylonitrile, and dienes having a chain structure, such as1,3-butadiene and 1,3-hexadiene; ternary copolymers of acrylonitrile,1,3-butadiene, and maleic anhydride; and copolymers obtained byhydrogenation of the diene portion of the above copolymers to a highdegree to convert the double bonds into saturated bonds.

The properties of the thermoplastic elastomer copolymer related to thepresent invention are not particularly limited. It is preferable thatthe copolymer has a Mooney viscosity of about 10 to 80 at 100° C., anelongation at break of 500% or more, and a glass transition temperatureof −20° C. or lower because the copolYmer contributes to softening ofthe material without decreasing heat resistance of the polypropyleneresin of component (A) and component (A′).

Among the above thermoplastic elastomer copolymers, elastomers ofcopolymers of ethylene and an α-olefin having 3 or more carbon atoms,elastomers of copolymers of ethylene, an α-olefin having 3 or morecarbon atoms, and a diene, elastomers of copolymers of styrene and adiene, and hydrogenation products of the elastomers of copolymers ofstyrene and a diene are preferable from the standpoint of flexibility,moldability, and heat resistance. The thermoplastic elastomer copolymercan be used singly or as a combination of two or more types.

In the resin mixture of component (A) and component (B) in thedecorative film or sheet of the present invention or the resin mixtureof component (A′) and component (B) in the decorative building materialof the present invention, it is preferable that the content of thepolypropylene resin of component (A) or component (A′) is 60% by weightor more, and the content of the thermoplastic elastomer copolymer ofcomponent (B) is 40% by weight or less. It is more preferable that thecontent of the polypropylene resin of component (A) or component (A′) is99 to 60% by weight, and the content of the thermoplastic elastomercopolymer of component (B) is 1 to 40% by weight or less. When thecontent of the thermoplastic elastomer copolymer exceeds 40% by weight,transparency becomes inferior, and flexibility is exhibited excessively.

In the decorative film or sheet of the present invention, the film orthe sheet comprising the polypropylene resin of component (A) or theresin mixture comprising the polypropylene resin of component (A) andthe thermoplastic elastomer copolymer of component (B) is used for asurface layer or a surface layer and a substrate. When the film or thesheet is used for molding, where desired, process oils, otherthermoplastic resins, modified polyolefins, various stabilizers,inorganic or organic fillers, antistatic agents, chlorine scavengers,antiblocking agents, anticlouding agents, organic flame retardants,auxiliary flame retardants, auxiliary agents for working, bloomingsuppressors, and waxes may be added to the polypropylene resin or theresin mixture within the range that the object of the present inventionis not adversely affected.

As the process oil, softeners used in processing of synthetic rubber canbe used without modification. Particularly in processing of the resinmixture, movement of molecules of the thermoplastic elastomer copolymerduring mixing of the two components is facilitated by using the processoil, and generation of heat by internal friction during the mixingdecreases. Moreover, workability during molding, flexibility of themolded product, tensile strength, and friction resistance of component(A) and the resin mixture are improved by using the process oil.

As the process oil, any mineral oil or synthetic oil can be used.Specific examples of the mineral oil include distillates obtained byatmospheric distillation of paraffinic crude oils, intermediate crudeoils and naphthenic crude oils, refined oils as a fraction obtained byvacuum distillation of a residual oil obtained in the atmosphericdistillation, and deeply dewaxed oils. Examples of the synthetic oilinclude alkylbenzenes, polybutene, and poly(α-olefin).

The properties of the process oil used in the present invention are notparticularly limited. Particularly in mixing of the two components ofthe resin mixture, process oils preferably having a kinematic viscosityof 10 to 1000 cSt, more preferably 20 to 700 cSt, are used.

Examples of the other thermoplastic resin described above include lowdensity polyethylene produced by the high pressure process, high densitypolyethylene, other types of polypropylene, polybutene, polyvinylchloride, polystyrene, and polyamide. Examples of the otherthermoplastic resin also include linear copolymers of ethylene and anα-olefin which are not used as the thermoplastic elastomer copolymer inthe resin mixture, such as copolymers of ethylene and butene-1,copolymers of ethylene and hexene-1, copolymers of ethylene andoctene-1, acrylic resins, ABS resins, polyesters, and polycarbonates.

Among these resins, polyolefin resins, such as various types ofpolyethylene, other types of polypropylene, and polybutene, arepreferable from the standpoint of compatibility, and polyethylene andcopolymers of ethylene and α-olefins are more preferable.

Examples of the modified polyolefin include polymers obtained bychemical modification of polyolefins, such as polyethylene,polypropylene, copolymers of ethylene and α-olefins, copolymers ofethylene, α-olefins, and conjugated diene compounds such as EPDM, andrubbers of copolymers of ethylene, aromatic monovinyl compounds, andconjugated diene compounds, with unsaturated carboxylic acids, such asacrylic acid, methacrylic acid, and maleic acid, anhydrides ofunsaturated carboxylic acids, such as maleic anhydride, esters ofunsaturated carboxylic acids, such as methyl acrylate and monomethylmaleate, amides of unsaturated carboxylic acids, such as acrylamide andmaleic acid monoamide, or imides of unsaturated carboxylic acids, suchas maleimide and N-butylmaleimide.

For the chemical modification, for example, the polyolefin is reactedwith the above unsaturated carboxylic acid or a derivative thereof usinga radical generator such as benzoyl peroxide in a suitable solvent.

As the above stabilizer, stabilizers to prevent oxidation and heatdegradation are generally used. For example, phenolic stabilizers,organic phosphite stabilizers, thioether stabilizers, and hindered aminestabilizers can be used.

As the phenolic stabilizers, conventional phenolic stabilizers can beused. Examples of the phenolic stabilizer include2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol,2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol,2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol,2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol,2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-5-t-hexylphenol,2-cyclohexyl-4-n-butyl-6-isopropylphenol, mixed cresols modified withstyrene, dl-α-tocopherol, t-butylhydroquinone,2,2′-methylenebis(4-methyl-6-t-butylphenol),4,4′-butylidenebis(3-methyl-6-t-butylphenol),4,4′-thiobis(3-methyl-6-t-butylphenol),2,2′-thiobis(4-methyl-6-t-butylphenol),4,4′-methylenebis(2,6-di-t-butylphenol),2,2′-methylenebis[6-(1-methylcyclohexyl)-p-cresol],2,2′-ethylidenebis(4,6-di-t-butylphenol),2,2′-butylidenebis(2-t-butyl-4-methylphenol),1,1,2tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, triethyleneglycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],2,2′-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],N,N′-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamide),3,5-di-t-butyl-4-hydroxybenzyl phosphonate diethyl ester,1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate,1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate,tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate,2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine,tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,bis(3,5-di-t-butyl-4-hydroxybenzyl ethyl phosphonate)calcium,bis(1,3,5-di-t-butyl-4-hydroxybenzyl ethyl phosphonate) nickel,bis[3,3-bis(3-t-butyl-4-hydroxyphenyl)butyric acid]glycol ester,N,N′-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine,2,2′-oxamidobis[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate],bis[2-t-butyl-4-methyl-6-(3-t-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate,1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxyphenyl)benzene,3,9-bis[1,1-dimethyl-2-[β-(3,t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl-2,4,8,10-tetraoxaspiro[5,5]undecane,2,2-bis[4-[2-(3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)]ethoxyphenyl]propane,stearyl-β-(4-hydroxy-3,5-di-t-butylphenol)propionate, and otherβ-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl esters. Amongthese compounds, 2,6-di-t-butyl-4-methylphenol,stearyl-β-(4-hydroxy-3,5-di-t-butylphenol)propionate,2,2′-ethylidenebis(4,6-di-t-butylphenol), andtetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methaneare preferable.

Examples of the organic phosphite stabilizer include trioctyl phosphite,trilauryl phosphite, tristridecyl phosphite, trisisodecyl phosphite,phenyl diisooctyl phosphite, phenyl di(tridecyl)phosphite, diphenylisooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecylphosphite, triphenyl phosphite, tris(nonylphenyl)phosphite,tris(2,4-di-t-butylphenyl)phosphite, tris(butoxyethyl)phosphite,tetratridecyl 4,4′-butylidenebis(3-methyl-6-t-butylphenol)diphoshpite,4,4′-isopropylidenediphenol alkyl phosphite containing an alkyl grouphaving about 12 to 15 carbon atoms,4,4′-isopropylidenebis(2,4-t-butylphenol)di(nonylphenyl)phosphite,tris(biphenyl)phosphite, tetra(tridecyl)1,1,3-tris(2-methyl-5-t-butyl-4-hydroxyphenyl)butane diphosphite,tris(3,5-di-t-butyl-4-hydroxyphenyl)phosphite, hydrogenated4,4′-isopropylidenediphenol polyphosphite,bis(octylphenyl)bis[4,4′-butylidenebis(3-methyl-6-t-butylphenol)]1,6-hexanedioldiphosphite, hexatridecyl1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenol)diphosphite,tris[4,4′-isopropylidenebis(2-t-butylphenol)]phosphite,tris(1,3-distearoyloxyisopropyl)phosphite,9,10-dihydro-9-phosphaphenanthrene-10-oxide,tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylene diphosphonite, distearylpentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite,phenyl 4,4′-isopropylidenediphenol pentaerythritol diphosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, andphenyl bisphenol A pentaerythritol diphosphite.

Among these compounds, tris(2,4-di-t-butylphenyl)phosphite,tris(nonylphenyl)phosphite, and tetrakis(2,4-di-t-butylphenyl)4,4′-biphenylene diphosphite are preferable, andtris(2,4-di-t-butylphenyl)phosphite is more preferable.

As the organic thioether stabilizer, dialkyl thiodipropionates andpolyhydric alcohol esters of alkylthiopropionic acids are preferablyused. As the above dialkyl thiodipropionate, dialkyl thiodipropionatescontaining alkyl groups having 6 to 20 carbon atoms are preferable. Asthe above polyhydric alcohol esters of alkylthiopropionic acids,polyhydric alcohol esters of alkylthiopropionic acids containing analkyl group having 4 to 20 carbon atoms are preferable. Examples of thepolyhydric alcohol constituting the polyhydric alcohol ester includeglycerol, trimethylolethane, trimethylolpropane, pentaerythritol, andtrishydroxyethyl isocyanurate.

Examples of the dialkyl thiodipropionate include dilaurylthiodipropionate, dimyristyl thiodipropionate, and distearylthiodipropionate. Examples of the polyhydric alcohol ester of analkylthiopropionic acid include glycerol tributylthiopropionate,glycerol trioctylthiopropionate, glycerol trilaurylthiopropionate,glycerol tristearylthiopropionate, trimethylolethanetributylthiopropionate, trimethylolethane trioctylthiopropionate,trimethylolethane trilaurylthiopropionate, trimethylolethanetristearylthiopropionate, pentaerythritol tetrabutylthiopropionate,pentaerythritol tetraoctylthiopropionate, pentaerythritoltetralaurylthiopropionate, and pentaerythritoltetrastearylthiopropionate. Among these compounds, dilaurylthiodipropionate, distearyl thiodipropionate, and pentaerythritoltetralaurylthiopropionate are preferable.

Examples of the hindered amine stabilizer includebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, polycondensation productsof dimethyl succinate and1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine,poly[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl][(2,2,6,6,-tetramethyl-4-piperidyl)imino]hexamethylene[2,2,6,6,-tetramethyl-4-piperidyl)imino],tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis(1,2,6,6-tetramethyl-4-piperidyl)2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate,bis(N-methyl-2,2,6,6,-tetramethyl-4-piperidyl)sebacate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperadinone), (mixed2,2,6,6-tetramethyl-4-piperidyl/tridecyl)1,2,3,4-butanetetracarboxylate, (mixed1,2,2,6,6-pentamethyl-4-piperidyl/tridecyl)1,2,3,4-butanetetracarboxylate, mixed[2,2,6,6-tetramethyl-4-piperidyl/β,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl]1,2,3,4-butanetetracarboxylate,mixed [1,2,2,6,6-pentamethyl4-piperidyl/β,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl 1,2,3,4-butanetetracarboxylate,condensation products of N,N′-bis(3-aminopropyl)-ethylenediamine and2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine,poly[6-N-morpholyl-1,3,5-triazine-2,4-diyl][2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imide],condensation products ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and1,2-dibromoethane, and[N-(2,2,6,6-tetramethyl-4-piperidyl)-2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)imino]propionamide.

Among these hindered amine stabilizers, polycondensation products ofdimethyl succinate and1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine,poly[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl][(2,2,6,6,-tetramethyl-4-piperidyl)imino]hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino],tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis(1,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperadinone), (mixed2,2,6,6-tetramethyl-4-piperidyl/tridecyl)1,2,3,4-butanetetracarboxylate, (mixed1,2,2,6,6-pentamethyl-4-piperidyl/tridecyl)1,2,3,4-butanetetracarboxylate, mixed[2,2,6,6-tetramethyl-4-piperidyl/β,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl]1,2,3,4-butanetetracarboxylate, mixed[1,2,2,6,6-pentamethyl-4-piperidyl/β,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethyl1,2,3,4-butanetetracarboxylate, condensation products ofN,N′-bis(3-aminopropyl)ethylenediamine and2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine,poly[6-N-morpholyl-1,3,5-triazine-2,4-diyl][2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imide],condensation products ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene-diamine and1,2-dibromoethane, and[N-(2,2,6,6-tetramethyl-4-piperidyl)-2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)imino]propionamideare preferable.

Examples of the inorganic filler include fillers having sphericalshapes, fillers having plate shapes, and fillers having fiber shapes.Examples of the filler having a spherical shape include calciumcarbonate, kaolin (aluminum silicate), silica, perlite, Shirasu balloon,sericite, diatomaceous earth, calcium sulfite, baked alumina, calciumsilicate, crystalline zeolite, and amorphous zeolite. Examples of thefiller having a plate shape include talc and mica. Examples of thefiller having a fiber shape include fillers having needle shapes, suchas wollastonite; fillers having fiber shapes, such as magnesiumoxysulfate, fiber of potassium titanate, and calcium carbonate having afiber shape; and fillers having a long fiber shape, such as glass fiber.

Examples of the organic filler include powder of wood materials, such aswood powder and cotton powder; powder of rice hulls; powder ofcrosslinked rubber; powder of plastics; and powder of colagen.

Examples of the fire retardant include hydrated aluminum, hydratedgypsum, zinc borate, barium borate, borax, kaolin, clay, calciumcarbonate, alunite, basic magnesium carbonate, calcium hydroxide, andmagnesium hydroxide. Among these fillers, fillers adversely affectingthe transparency are not used in surface layers but used mainly insubstrates.

In the decorative film or sheet of the present invention, for example, afilm or a sheet used for a surface layer or a surface layer and asubstrate is molded advantageously as follows. Various additives areoptionally added to the polypropylene resin of component (A).Alternatively, the thermoplastic elastomer copolymer of component (B)and, optionally, various additives are added to the polypropylene resinof component (A). A molding material is prepared by mixing thecomponents using a tumbler blender or a Henschel mixer; by melt kneadinga mixture of the components obtained above using a single screw extruderor a twin-screw extruder, and then pelletizing the kneaded mixture; orby melt mixing the components using a kneader or a Banbury mixer, andthen pelletizing the obtained mixture. The prepared molding material isformed into a film or a sheet having a thickness of 0.03 to 0.5 mm inaccordance with a molding process, such as the cast molding, theinflation molding, or the calender molding.

It is preferable that the film or the sheet thus prepared has a surfacetreatment, such as a treatment by corona discharge, a treatment withozone, and a treatment with plasma, to improve the property for adhesionor printing. When this film or sheet is used as a substrate, theshielding effect may be provided by addition of a pigment during themolding.

The decorative film or sheet of the present invention may be a so-calleddoubling film which has a laminate structure comprising a surface layer,an adhesive layer, a layer having a pattern, an adhesive layer, and asubstrate, or a so-called back printed film which has a laminatestructure comprising a surface layer, an adhesive layer, and a layerhaving a pattern but not comprising a substrate and has a patternprinted directly on a surface layer.

As the adhesive layer in the above decorative film or sheet, a layerhaving a thickness of 1 to 20 μm and made of, for example, aconventional adhesive material which comprises a polyurethane resin, anepoxy resin, an acrylic resin, a vinyl resin, a vinyl acetate resin, apolyester resin, an ethylene-vinyl acetate copolymer resin, an acrylicmonomer-vinyl acetate copolymer resin, a polyamide resin, or an ionomerresin as the main component or a modified polyolefin is preferably used.Examples of the modified polyolefin include polymers obtained bychemical modification of polyolefins, such as polyethylene,polypropylene, copolymers of ethylene and α-olefins, copolymers ofethylene, α-olefins, and conjugated diene compounds such as EPDM, andrubbers of copolymers of ethylene, aromatic monovinyl compounds, andconjugated diene compounds, with unsaturated carboxylic acids, such asacrylic acid, methacrylic acid, and maleic acid, anhydrides ofunsaturated carboxylic acids, such as maleic anhydride, esters ofunsaturated carboxylic acids, such as methyl acrylate and monomethylmaleate, amides of unsaturated carboxylic acids, such as acrylamide andmaleic acid monoamide, or imides of unsaturated carboxylic acids, suchas maleimide and N-butylmalemide.

The form of the adhesive material used in the working is notparticularly limited, and an adhesive of a liquid, an intermediate melt,a film, or a sheet can be used. When two adhesive layers are formed, thetwo adhesive layers may be composed of the same material or differentmaterials.

On the layer having a pattern, a pattern, such as a wood pattern, astone grain pattern, a surface pattern of natural leather, a clothpattern, and an abstract pattern, is printed. A binder contained in anink used for forming the pattern is not particularly limited, and forexample, any binder suitably selected from polyurethane resins, vinylchloride resins, vinyl chloride-vinyl acetate copolymer resins,combinations of vinyl chloride-vinyl acetate copolymer resins andacrylic resins, chlorinated polypropylene resins, acrylic resins,polyester resins, polyamide resins, butyral resins, polystyrene resins,nitrocellulose resins, and acetylcellulose resins can be used. The inksuitably comprises coloring agents such as pigments and dyestuffs,fillers, and solvents. The patterned layer generally has a thickness ofabout 1 to 5 μm.

It is preferable that the layer having a pattern in the decorative filmor sheet of the present invention has the two-layer structure comprisinga patterned layer and a shielding layer. As the ink used for forming theshielding layer, an ink prepared by suitably mixing coloring agents,such as pigments and dyes stuffs, fillers, solvents, stabilizers,plasticizers, catalysts, and curing agents with a binder is used.Examples of the binder include the same materials as those described asthe examples of the binder contained in the ink used for forming theabove patterned layer. The shielding layer is preferably a layer havinga thickness of 1 to 20 μm and covered with a uniform color. Theshielding layer is disposed under the patterned layer.

The decorative film or sheet of the present invention may comprise,where desired, a top coat layer which has a thickness of about 1 to 20μm, is made of an acrylic resin or a polyurethane resin, and is disposedon the surface layer to improve abrasion resistance, weatheringresistance, workability for embossing, scratch resistance, and foulingresistance. The surface layer may be embossed or has a wiping ink filledin concave portions. One or more layers of an adhesive resin may beformed between the surface layer and the adhesive layer, where desired.Examples of the adhesive resin used for the layer of an adhesive resininclude ethylene-vinyl acetate copolymers (EVA), ethylene-methylmethacrylate copolymers (EMMA), and the polyolefins modified withunsaturated carboxylic acids or derivatives of these acids describedabove. In this case, it is advantageous that a multi-layer film or sheetis prepared by multi-layer extrusion of the above polypropylene resin orthe above resin mixture used as the surface layer and the adhesiveresin, and the prepared multi-layer film or sheet is used for producingthe decorative film or sheet.

As the process for producing the decorative film or sheet of the presentinvention, any process can be used as along as the film or the sheethaving the above laminate structure can be obtained. For example, it isadvantageous that a film or a sheet having the structure comprising asurface layer, an adhesive layer, a layer having a pattern, an adhesivelayer, and a substrate is produced in accordance with one of thefollowing two processes.

In the first process, an adhesive layer, a layer having a pattern, andanother adhesive layer are successively laminated together by aconventional method of printing, such as the gravure printing, thescreen printing, the offset printing, and the flexo printing. Then, (1)a film or a sheet forming a surface layer is laminated with the formedadhesive layer by heat lamination; (2) a film or a sheet forming asurface layer is laminated with the formed adhesive layer by drylamination or wet lamination; (3) a film or a sheet forming a surfacelayer is coated with an adhesive layer having the same composition asthat of the above layers in accordance with a conventional method ofprinting, such as the gravure printing, the screen printing, the offsetprinting, and the flexo printing, and the coated film or sheet is thenlaminated with the adhesive layer of the above laminate by heatlamination in such a manner that the adhesive layers are attachedtogether; or (4) a surface layer is formed on the formed adhesive layerby extrusion lamination of a resin forming the surface layer.

In the second process, an adhesive layer and a layer having a patternare successively laminated on a substrate by a conventional method ofprinting, such as the gravure printing, the screen printing, the offsetprinting, and the flexo printing. Then, (1) an adhesive layer is formedon a film or a sheet forming a surface layer using a conventional methodof printing, such as the gravure printing, the screen printing, theoffset printing, and the flexo printing or a coating method, such as theroll coating, and the obtained laminate is then laminated with thelaminate prepared above by heat lamination in such a manner that theadhesive layer is attached to the layer having a pattern; (2) a film ora sheet forming the surface layer is coated with an adhesive layer andthen laminated with the laminate prepared above by dry lamination or wetlamination in the same manner as that conducted above in (1); (3) aresin forming an adhesive layer is extruded between the layer having apattern and a film or a sheet forming a surface layer in a meltcondition to form a laminate (extrusion lamination); or (4) the adhesivelayer and the surface layer are formed simultaneously by directlamination by coextrusion of the adhesive layer and a resin forming asurface layer.

The present invention also provides a decorative material obtained bylaminating the film or the sheet thus obtained with various types ofsubstrate.

Examples of the substrate used for the decorative material includesubstrates of woods, such as wood, ply wood, laminated wood, andparticle boards; substrates of metals, such as steel plates, stainlesssteel plates, and aluminum plates; inorganic substrates, such as gypsumboards; and substrates of resins, such as flexible polypropylene andpolyethylene.

To produce the decorative material, the decorative film or sheet islaminated with the substrate using an adhesive material in such a mannerthat the substrate and the layer having a pattern are faced to eachother. The adhesive material used in this process is not particularlylimited and can suitably be selected from conventional adhesivematerials.

The decorative building material of the present invention generally hasa structure comprising a surface layer made of the polypropylene resinof component (A) or the resin mixture comprising the polypropylene resinof component (A) and the thermoplastic elastomer copolymer of component(B) and a backing material laminated to the back face of the surfacelayer. The method for preparing a molded article used for the surfacelayer (hereinafter, referred to as a material of a surface layer) is notparticularly limited and can suitably selected in accordance with thetype of the decorative building material. For example, when thedecorative building material has a stone grain pattern, it isadvantageous that the polypropylene resin of component (A′) describedabove or the resin mixture described above which relates to the presentinvention (hereinafter, referred to as the base resin of the presentinvention) and chips of a polyester resin such as polyethyleneterephthalate or rubber are mixed together using mixing rolls, and theobtained mixture is formed into a sheet. The chips may be colored.

When the decorative building material is a material of a sliced tiletype, for example, it is advantageous that the base resin of the presentinvention and, optionally, other flexible polypropylene resins areplaced into a specific mold to prepare a plate by press molding, and theprepared plate is cut to a specific thickness. As the flexiblepolypropylene resin, the same resins as those described below asexamples of the flexible polypropylene resin used for the backingmaterial can be used. When the decorative building material is amaterial of a marble type, for example, coloring agents, such asinorganic pigments and organic pigments, are mixed with the base resinof the present invention in suitable amounts, and the prepared mixturecan be formed into a plate by the injection molding or into a sheet bythe cast molding. When the decorative building material is a material ofa back printed type, for example, the base resin of the presentinvention is formed into a sheet by the cast molding, and print is madeon the back face of the prepared sheet to provide a pattern.

Materials of a surface layer prepared by mixing chips of fibers, such ascolored polyester fibers or cellulose fibers such as rayon fibers, withthe base resin of the present invention, followed by molding theprepared mixture into a plate or materials of a surface layer havingemboss or print on the surface may also be used.

The thickness of the above material of a surface layer is notparticularly limited and generally selected in the range of 50 μm to 1mm in accordance with the situation.

The backing material is not particularly limited, and paper or othermaterials conventionally used as the backing material of plasticdecorative building materials can be used. Backing materials containinga flexible polypropylene resin as the main component are preferablyused.

As the flexible polypropylene resin used for the backing material, aflexible polypropylene resin having a tensile modulus of 600 MPa or lessis preferable. When the tensile modulus exceeds 600 MPa, a sheet made byusing the resin is excessively firm, and there is the possibility thatfeel becomes inferior. When the tensile modulus is excessively small,molding a sheet becomes difficult. The tensile modulus is morepreferably in the range of 400 to 300 MPa. The tensile modulus isobtained by the measurement in accordance with the tensile test ofJapanese Industrial Standard K7113 using a No. 2 dumbbell of JapaneseIndustrial Standard.

As the flexible polypropylene resin, for example, (x) a polypropyleneresin comprising one or both of a homopolymer of propylene and acopolymer of propylene containing 4% by weight or less of units of otherolefins, wherein the homopolymer and the copolymer have [i] a pentadfraction expressed by rrrr/(1−mmmm)×100 of 15 to 60%, preferably 20 to60%, more preferably 25 to 55%, as measured by ¹³C-NMR, [ii] a peaktemperature of melting (Tm) of 150° C. or higher, preferably 150 to 165°C., as measured by DSC, and [iii] an enthalpy of melting (ΔH) of 100 J/gor less, preferably 20 to 100 J/g, more preferably 30 to 70 J/g, asmeasured by DSC, or (y) a mixture comprising the above polypropyleneresin and a random copolymer of propylene containing units of olefinsother than propylene is preferable.

The above rrrr/(1−mmmm)×100, the peak temperature of melting as measuredby DSC, and the enthalpy of melting (ΔH) as measured by DSC are the sameas those described for the polypropylene resin of component (A).

The content of the random copolymer of propylene containing units ofolefins other than propylene in the above mixture of component (y) isgenerally 90 to 5% by weight, preferably 70 to 5% by weight. When thecontent exceeds 90% by weight, the properties of the flexiblepolypropylene resin are not sufficiently exhibited.

In the random copolymer of propylene containing units of olefins otherthan propylene which is used in the mixture of component (y), examplesof the olefin used as the comonomer forming the unit of an olefin otherthan propylene include ethylene, butene-1, pentene-1,4-methyl-1-pentene, hexene-1, heptene-1, octene-1, nonene-1, anddecene-1. The above comonomer can be used singly or as a combination oftwo or more types. The content of the units of olefins other thanpropylene in the random copolymer is generally in the range of 10 to 70%by weight.

The polypropylene resin of component (x) can be produced in accordancewith the same procedures as those for producing the polypropylene resinused in the surface layer. On the other hand, the mixture of component(y) can be prepared in accordance with a two stage polymerizationprocess in which a polypropylene resin is produced in the first stage inthe same manner as that described above, and the copolymerization witholefins other than propylene is conducted in the second stage. Ofcourse, the mixture of component (y) can also be produced by separatelyproducing the polypropylene resin and a random copolymer of propylenecontaining units of olefins other than propylene, followed by blendingthe resin and the copolymer produced.

The backing material used in the decorative building material of thepresent invention can be produced, for example, by preparing a resincomposition comprising 4 to 45% by weight of (W) the above flexiblepolypropylene resin, 2 to 50% by weight of (X) an elastomer, 10 to 70%by weight of (Y) an inorganic filler containing hydroxyl group, and 0 to40% by weight of (Z) other fillers, followed by forming the preparedresin composition into a sheet.

The above elastomer used as component (X) is not particularly limited,and various elastomers can be used. Styrene elastomers and olefinelastomers are preferable. Examples of the styrene elastomer includestyrene-butadiene block copolymers (SBR), styrene-butadiene-styreneblock copolymers (SBS), hydrogenated styrene-butadiene-styrene blockcopolymers (SEBS), styrene-isoprene block copolymers (SIR),styrene-isoprene-styrene block copolymers (SIS), and hydrogenatedstyrene-isoprene-styrene block copolymers (SEPS). Examples of the olefinelastomers include ethylene-propylene rubber (EPR),ethylene-propylene-diene rubber (EPDM), and ethylene-butylene rubber(EBM).

The elastomer can be used singly or as a combination of two or moretypes. When a styrene elastomer is used, a combined use of SEBS andother styrene elastomers is preferable.

In the resin composition, the inorganic filler containing hydroxyl groupused as component (Y) is not particularly limited, and fillerscontaining hydroxyl group or water molecules in the molecule can beused. Examples of the inorganic filler containing hydroxyl group includealuminum hydroxide, magnesium hydroxide, potassium hydroxide, bariumhydroxide, hydrated alumina, hydrated gypsum, zinc borate, bariumborate, borax, alunite, and basic magnesium carbonate. Among thesecompounds, aluminum hydroxide and magnesium hydroxide are preferable.The filler containing hydroxyl group can be used singly or as acombination of two or more types.

It is preferable that the components are comprised in the resincomposition in the following amounts: the flexible polypropylene resinof component (W), in the range of 4 to 45% by weight; the elastomer ofcomponent (X), in the range of 2 to 50% by weight; and the inorganicfiller containing hydroxyl group of component (Y), in the range of 10 to70% by weight. When the amount of component (W), (X), or (Y) is outsidethe above range, it is difficult to obtain a resin composition havingexcellent balance between resistance to blocking, resistance toslipping, and workability in molding. To obtain a resin compositionhaving excellent balance between resistance to blocking, resistance toslipping, and workability in molding, the amount of component (W) in therange of 5 to 40% by weight, the amount of component (X) in the range of5 to 40% by weight, and the amount of component (Y) in the range of 20to 60% by weight are more preferable. Component (W) comprised in theresin composition exhibits an effect of increasing the range of themoldable temperature.

Where desired, this resin composition may also comprise other fillers inan amount of about 40% by weight or less as component (Z) to provide thebacking material with a suitable stiffness. When the amount of component(Z) exceeds 40% by weight, the molding property becomes inferior, andthere is the possibility that flexibility deteriorates. To provide theresin composition with a suitable stiffness without adversely affectingthe molding property and flexibility, it is preferable that component(Z) is comprised in an amount of 30% by weight or less.

As the other filler, inorganic fillers and organic fillers other thanthe above inorganic filler containing hydroxyl group can be used.Examples of the inorganic filler other than the inorganic fillercontaining hydroxyl group include fillers having spherical shapes,fillers having plate shapes, and fillers having fiber shapes. Examplesof the filler having a spherical shape include calcium carbonate, kaolin(aluminum silicate), silica, perlite, Shirasu balloon, sericite,diatomaceous earth, calcium sulfite, baked alumina, calcium silicate,crystalline zeolite, and amorphous zeolite. Examples of the fillerhaving a plate shape include talc and mica. Examples of the fillerhaving a fiber shape include fillers having needle shapes, such aswollastonite; fillers having fiber shapes, such as magnesium oxysulfate,fiber of potassium titanate, and calcium carbonate having a fiber shape;and fillers having a long fiber shape, such as glass fiber. Inorganiccoloring agents, such as carbon black, can also be used.

Examples of the organic filler include powder of wood materials, such aswood powder and cotton powder; powder of rice hulls; powder ofcrosslinked rubber; powder of plastics; and powder of colagen.

Among these fillers, inorganic fillers are preferably used. The fillercan be used singly or as a combination of two or more types.

The process for preparing the resin composition is not particularlylimited, and a conventional process can be used. For example, the resincomposition can be prepared by melt mixing the flexible polypropyleneresin of component (W), the elastomer of component (X), the inorganicfiller containing hydroxyl group of component (Y), and other fillers ofcomponent (Z) and, optionally, various additives using a batch mixer,such as Banbury mixer, or a kneader-extruder, such as a twin-screwkneader, a twin-screw extruder, and a single screw extruder, followed bygranulating the prepared mixture, where desired. When the components aresupplied into a kneader-extruder, the entire amount of the componentsmay be blended in advance and supplied into the kneader-extruder, or thecomponents may be supplied separately into the kneader-extruder.

The backing material can be prepared by forming thus prepared resincomposition into a sheet. The process for forming the sheet is notparticularly limited, and a conventional extrusion process, such as theT-die molding, can be used. However, it is preferable that the resincomposition obtained after the melt kneading is directly supplied tomixing rolls, calender rolls, or rolls for forming sheets, to prepare asheet having a prescribed thickness. The resin composition obtained bythe melt kneading may be directly formed into a sheet withoutgranulation after the extrusion. Alternatively, the resin compositionmay be granulated into pellets, and the prepared pellets are formed intoa sheet by extrusion using various extruders.

The thickness of the thus obtained backing material is not particularlylimited and, in general, suitably selected in the range of 0.1 to 50 mmin accordance with the situation.

The material of a surface layer and the backing material used in thedecorative building material of the present invention may comprise,where desired, process oils, other thermoplastic resins, modifiedpolyolefins, various stabilizers, lubricants, antistatic agents,chlorine scavengers, flame retardants, auxiliary flame retardants,antiblocking agents, auxiliary agents for working, bleeding suppressors,and coloring agents.

The material of a surface layer may also comprise inorganic or organicfillers other than the fillers described above, where desired.

Examples of the process oil, the other thermoplastic resins, themodified polyolefin, various types of the stabilizer, the inorganicfillers, the organic fillers, and the flame retardants includecorresponding compounds and materials described above as the examples inthe decorative film or sheet.

The decorative building material of the present invention may beprepared by laminating a surface layer and a backing material by heatsealing or by laminating a surface layer and a backing layer with anadhesive layer placed between them. When an adhesive layer is placed, alayer made of, for example, a conventional adhesive material whichcomprises a polyurethane resin, an epoxy resin, an acrylic resin, avinyl resin, a vinyl acetate resin, a polyester resin, an ethylene-vinylacetate copolymer resin, an acrylic monomer-vinyl acetate copolymerresin, a polyamide resin, or an ionomer resin as the main component or amodified polyolefin is preferably used as the adhesive layer.

In the decorative building material of the present invention, wheredesired, layers comprising various materials, such as sheets containingcolored fibers, sheets of glass fiber, paper, and non-woven fabrics, maybe formed between the surface layer and the backing material, or betweenthe surface layer and the adhesive layer when the adhesive layer isplaced, to improve the property to form a pattern or strength. Atransparent protective layer may be formed on the surface layer, wheredesired. Examples of the protective layer include layers comprising anacrylic resin curable by ultraviolet light and foamed layers.

In accordance with the present invention, a laminated decorative film orsheet which comprises a surface layer having excellent transparency andhardness, has excellent workability in bending, V-cutting, and lapping,and does not cause problems in disposal and a decorative buildingmaterial which has excellent heat resistance, weatherability, andabrasion resistance, provides soft feeling, and does not cause problemsin the environment can be obtained easily.

The present invention is described more specifically with reference toexamples in the following. However, the present invention is not limitedby the examples.

<Production of Decorative Sheets or Films>

EXAMPLE 1

(1) Production of a Homopolymer of Propylene

{1} Preparation of a Magnesium Compound

Into a glass reactor which had an inner volume of about 6 liters, wasequipped with a stirrer, and had been sufficiently purged with nitrogengas, about 2,430 g of ethanol, 20 g of iodine, and 160 g of magnesiummetal were placed. The obtained mixture was heated while being stirredto allow the reaction to proceed in the mixture under a refluxingcondition until hydrogen gas was not generated any more in the reactionsystem, and a solid reaction product was produced. By drying theobtained reaction mixture containing the solid reaction product under avacuum, a magnesium compound was obtained.

{2} Preparation of a Solid Catalyst Component of Component (a)

Into a glass reactor which had an inner volume of 5 liters and had beensufficiently purged with nitrogen gas, 160 g of the above magnesiumcompound obtained in {1} (not pulverized), 800 ml of purified heptane,24 ml of silicon tetrachloride, and 23 ml of diethyl phthalate wereplaced, and the reaction system was kept at 80° C. While the reactionsystem was stirred, 770 ml of titanium tetrachloride was added into thesystem, and the reaction was allowed to proceed at 110° C. for 2 hours.Then, the solid component was separated and washed with purified heptaneat 90° C. To the washed solid component, 1,220 ml of titaniumtetrachloride was added, and the reaction was allowed to proceed at 110°C. for 2 hours. The solid component was washed sufficiently withpurified heptane to obtain a solid catalyst component of component (a).

{3} Gas Phase Polymerization

Into a polymerization reactor having an inner volume of 200 liters,components were supplied at the following rates: the above solidcatalyst component of component (a) obtained in {2}, 6.0 g/hour;triisobutylaluminum (TIBA), 0.2 mol/hour; 1-allyl-3,4-dimethoxybenzene(ADMB), 0.006 mol/hour; cyclohexylmethyldimethoxysilane (CHMDMS), 0.03mol/hour; and propylene, 43 kg/hour. The polymerization was allowed toproceed at 70° C. and 28 kg/cm²G. The rate of formation of the polymerwas 30 kg/hour.

The polymer obtained by the above polymerization was a homopolymer ofpropylene having an intrinsic viscosity [η] (135° C., in decaline) of5.04 dl/g.

The above homopolymer contained 88.1% by weight of a fraction insolublein boiling n-heptane which had [η] of 5.42 dl/g and a fraction solublein boiling n-heptane which had [η] of 2.07 dl/g.

The homopolymer had a pentad fraction expressed by rrrr/(1−mmmm)×100 of24.2% as calculated from ¹³C-NMR, a peak temperature of melting (Tm) of158.7° C. as measured by DSC, and an enthalpy of melting (ΔH) of 80.7J/g as measured by DSC. With respect to the head-to-tail bonding ofpropylene, no reversed bonding was found. To powder of the obtainedpolypropylene, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane was mixed, andthen an antioxidant, a heat stabilizer, and a chlorine scavenger wereadded. The obtained mixture was extruded through a 40 mmφ extruder toobtain pellets. The obtained pellets had a melt index (MI) of 2.5 g/10minutes.

The above polymer was decomposed with a peroxide to obtain a lowmolecular weight polymer. The obtained low molecular weight polymershowed no change in the pentad fraction, the peak temperature ofmelting, or the enthalpy of melting from those of the original polymer.

(2) Molding of a Film of a Surface Layer

The pellets of the homopolymer of propylene obtained in (1) was formedinto a film having a thickness of 100 μm using a 90 mmφ cast moldingmachine under the condition of a resin temperature of 250° C. and apulling speed of 10 m/minute. At the time of molding, one face of thefilm was embossed, and both faces of the film were treated by coronadischarge (5.0 kW). The surface treated with the corona discharge had awetting index (obtained in accordance with the method of JapaneseIndustrial Standard K6768) of 50 dyne/cm.

(3) Lamination of an Adhesive Layer

An adhesive layer having a thickness of 3 μm was formed on the smoothface of the film obtained in (2) using a primer containing a vinylchloride-vinyl acetate copolymer resin as the main component inaccordance with the gravure printing.

(4) Preparation of a Printed Film (a Layer Having a Pattern)

A primer containing a vinyl chloride-vinyl acetate copolymer resin asthe main component and an ink containing a vinyl chloride-vinyl acetatecopolymer as the binder were successively laminated with a colored filmof high density polyethylene having a thickness of 90 μm in accordancewith the gravure printing. On the prepared laminate, a primer containinga vinyl chloride-vinyl acetate copolymer resin as the main component waslaminated in the same manner to prepare a printed film. The totalthickness of the printed film was 100 μm.

(5) Lamination of the Film of the Surface Layer and the Printed Film

The face having the adhesive layer of the above film of the surfacelayer obtained in (3) and the face having the adhesive layer of theabove printed film obtained in (4) were placed together, and both filmswere laminated by passing through rolls heated to 120° C. to obtain adecorative sheet,

(6) Lamination with Boards and Evaluation of Workability in Fabrication

In the decorative film obtained above, the surface layer showedexcellent transparency, and the layer having a pattern provided depth.The decorative film had the same degree of flexibility as that ofdecorative films made of polyvinyl chloride.

Using an adhesive material containing an ethylene-vinyl acetatecopolymer resin as the main component, the above decorative film waslaminated with a particle board having an intermediate density and arough surface in such a manner that the layer of the colored film ofhigh density polyethylene was in contact with the particle board. Thedecorative film was also laminated with a board having a flat surface inthe same manner. Both boards prepared above were worked by V-cutting.Neither formation of cracks nor whitening was observed at the foldedpart, and workability in lapping and V-cutting was excellent.

EXAMPLE 2

(1) Direct Lamination by Colamination

The homopolymer of propylene obtained in Example 1 (1) and an adhesiveresin prepared by mixing 20% by weight of a polyolefin modified withmaleic anhydride (manufactured by IDEMITSU PETROCHEMICAL Co., Ltd.,POLYTAC E-100) with 80% by weight of this homopolymer of propylene werecoextruded. The obtained laminate was treated with ozone and thenlaminated with the printed film obtained in Example 1 (4) to obtain adecorative film. The temperature of the resin at the time of extrusionwas 290° C., and the thickness of the obtained decorative film was 160μm.

(2) Lamination with Boards and Evaluation of Workability in Fabrication

In the decorative film obtained above, the surface layer showedexcellent transparency, and the layer having a pattern provided depth.The decorative film had the same degree of flexibility as that ofdecorative films made of polyvinyl chloride.

Using an adhesive material containing an ethylene-vinyl acetatecopolymer resin as the main component, the above decorative film waslaminated to a particle board having an intermediate density and a roughsurface in such a manner that the layer of the colored film of highdensity polyethylene was in contact with the particle board. Thedecorative film was also laminated to a board having a flat surface inthe same manner. Both boards prepared above were worked by V-cutting.Neither formation of cracks nor whitening was observed at the foldedpart, and workability in lapping and V-cutting was excellent.

EXAMPLE 3

(1) Preparation of a Film Printed on the Back

The film obtained in Example 1 (2) was used as the surface layer. On thesmooth face of this film, an adhesive layer and a layer having a patternwere successively laminated in accordance with the gravure printingusing a primer containing a vinyl chloride-vinyl acetate copolymer resinas the main component and an ink containing a vinyl chloride-vinylacetate copolymer resin as the binder. Using a mixture of a pigment withthe above ink, a uniformly colored layer was laminated with the obtainedlaminate in accordance with the gravure printing to prepare a decorativefilm.

(2) Lamination with Boards and Evaluation of Workability in Fabrication

In the decorative film obtained above, the surface layer showedexcellent transparency, and the layer having a pattern provided depth.The decorative film had the same degree of flexibility as that ofdecorative films made of polyvinyl chloride.

Using an adhesive material containing an ethylene-vinyl acetatecopolymer resin as the main component, the above decorative film waslaminated to a particle board having an intermediate density and a roughsurface in such a manner that the uniformly colored layer was in contactwith the particle board. The decorative film was also laminated to aboard having a flat surface in the same manner. Both boards preparedabove were worked by V-cutting. Neither formation of cracks norwhitening was observed at the folded part, and workability in lappingand V-cutting was excellent.

Comparative Example 1

(1) Preparation of a Film of a Surface Layer

A polypropylene resin (manufactured by SUMITOMO CHEMICAL Co., Ltd.;NOBLEN FL6315G; peak temperature of melting (Tm), 140° C.) in an amountof 90% by weight and 10% by weight of a thermoplastic elastomer(manufactured by KURARAY Co., Ltd.; HYBRAR HVS-3) were dry blended, andthe obtained blend was used for molding under the condition of a resintemperature of 230° C. and a pulling speed of 5 m/minute using a 40 mmφcast molding machine to prepare a film having a thickness of 80 μm. Oneface of the prepared film was embossed, and both faces were treated bycorona discharge (4.5 kW). The wetting index of the surface treated bycorona discharge was 49 dyne/cm.

(2) Lamination of an Adhesive Layer

An adhesive layer having a thickness of 3 μm was formed on the smoothface of the film obtained in (1) using a primer containing a vinylchloride-vinyl acetate copolymer resin as the main component inaccordance with the gravure printing.

(3) Preparation of a Printed Film (a Layer Having a Pattern)

A primer containing a vinyl chloride-vinyl acetate copolymer resin asthe main component and an ink containing a vinyl chloride-vinyl acetatecopolymer as the binder were successively laminated with a colored filmof high density polyethylene having a thickness of 90 μm in accordancewith the gravure printing. On the prepared laminate, a primer containinga vinyl chloride-vinyl acetate copolymer resin as the main component waslaminated in the same manner to prepare a printed film. The totalthickness of the printed film was 100 μm.

(4) Lamination of the Film of the Surface Layer and the Printed Film

The face having the adhesive layer of the above film of the surfacelayer obtained in (2) and the face having the adhesive layer of theabove printed film obtained in (3) were placed together, and both filmswere laminated by passing through rolls heated to 120° C. to obtain adecorative sheet,

(6) Lamination with Boards and Evaluation of Workability in Fabrication

In the decorative film obtained above, the surface layer showed slightlyinferior transparency, and the layer having a pattern provided depth.The decorative film had the same degree of flexibility as that ofdecorative films made of polyvinyl chloride.

Using an adhesive material containing an ethylene-vinyl acetatecopolymer resin as the main component, the above decorative film waslaminated to a particle board having an intermediate density and a roughsurface in such a manner that the layer of the colored film of highdensity polyethylene was in contact with the particle board. Thedecorative film was also laminated to a board having a flat surface inthe same manner. Both boards prepared above were worked by V-cutting.Whitening was observed at the folded part in working of lapping andV-cutting at a low temperature.

The results obtained above are shown together in Table 1.

TABLE 1 Comparative Evaluation Example 1 Example 2 Example 3 Example 1Transparency of excellent excellent excellent slightly the surface layerinferior Workability excellent excellent excellent whitening at inlapping low temperature Workability excellent excellent excellentwhitening at in V-cutting low temperature

<Production of Decorative Building Materials>

Physical properties and “feel” of the obtained decorative buildingmaterials were evaluated in accordance with the following methods:

(1) Abrasion resistance (in accordance with the method of JapaneseIndustrial Standard K7205)

The abrasion resistance was evaluated in accordance with the Taberabrasion test using a floor material made of a polyvinyl chloride resin(Comparative Example 2) as the reference. The result was evaluated inaccordance with the following criteria:

Δ: The abraded amount was the same as the abraded amount of the floormaterial made of a polyvinyl chloride resin.

◯: The abraded amount was less than and ½ or more of the abraded amountof the floor material made of a polyvinyl chloride resin.

⊚: The abraded amount was less than ½ of the abraded amount of the floormaterial made of a polyvinyl chloride resin.

(2) Heat resistance (in accordance with the method of JapaneseIndustrial Standard K7206)

The heat resistance was evaluated from the Vicat softening point inaccordance with the following criteria:

Δ: The Vicat softening point was 100° C. or lower.

◯: The Vicat softening point was higher than 100° C. and 150° C. orlower.

(3) Weatherability (in accordance with the method of Japanese IndustrialStandard A1415)

The weatherability was evaluated from the appearance after about 500hours using a WS type apparatus in accordance with the followingcriteria:

Δ: Crazings, cracks, and discoloration found.

◯: No change

(4) Feel

“Feel” was evaluated from the feeling obtained by touching a material byhands in accordance with the following criteria:

Δ: Felt cold when touched by hands.

◯: Felt warm when touched by hands.

Preparation Example 1 Preparation of a Resin for a Surface Layer

(1) Preparation of a Magnesium Compound

Into a glass reactor which had an inner volume of about 6 liters, wasequipped with a stirrer, and had been sufficiently purged with nitrogengas, about 2,430 g of ethanol, 20 g of iodine, and 160 g of magnesiummetal were placed. The obtained mixture was heated while being stirredto allow the reaction to proceed in the mixture under a refluxingcondition until hydrogen gas was not generated any more in the reactionsystem, and a solid reaction product was produced. By drying theobtained reaction mixture containing the solid reaction product under avacuum, a magnesium compound was obtained.

(2) Preparation of a Solid Catalyst Component of Component (a)

Into a glass reactor which had an inner volume of 5 liters and had beensufficiently purged with nitrogen gas, 160 g of the above magnesiumcompound obtained in (1) (not pulverized), 800 ml of purified heptane,24 ml of silicon tetrachloride, and 23 ml of diethyl phthalate wereplaced, and the reaction system was kept at 80° C. While the reactionsystem was stirred, 770 ml of titanium tetrachloride was added into thesystem, and the reaction was allowed to proceed at 110° C. for 2 hours.Then, the solid component was separated and washed with purified heptaneat 90° C. To the washed solid component, 1,220 ml of titaniumtetrachloride was added, and the reaction was allowed to proceed at 110°C. for 2 hours. The solid component was washed sufficiently withpurified heptane to obtain a solid catalyst component of component (a).

(3) Gas Phase Polymerization

Into a polymerization reactor having an inner volume of 200 liters,components were supplied at the following rates: the above solidcatalyst component of component (a) obtained in (2), 6.0 g/hour;triisobutylaluminum (TIBA), 0.2 mol/hour; 1-allyl-3,4-dimethoxybenzene(ADMB), 0.007 mol/hour; cyclohexylmethyldimethoxysilane (CHMDMS), 0.03mol/hour; and propylene, 40 kg/hour. The polymerization was allowed toproceed at 70° C. and 28 kg/cm²G. The rate of formation of the polymerwas 30 kg/hour.

The polymer obtained by the above polymerization was a homopolymer ofpropylene having an intrinsic viscosity [η] (135° C., in decaline) of5.04 dl/g.

The above homopolymer contained 88.1% by weight of a fraction insolublein boiling n-heptane which had [η] of 5.42 dl/g and a fraction solublein boiling n-heptane which had [η] of 2.07 dl/g.

The homopolymer had a pentad fraction expressed by rrrr/(1−mmmm)×100 of27.2% as calculated from ¹³C-NMR, a peak temperature of melting (Tm) of161.7° C. as measured by DSC, and an enthalpy of melting (ΔH) of 75.5J/g as measured by DSC. With respect to the head-to-tail bonding ofpropylene, no reversed bonding was found. To powder of the obtainedpolypropylene, 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane was mixed, andthen an antioxidant, a heat stabilizer, and a chlorine scavenger wereadded. The obtained mixture was extruded through a 40 mmφ extruder toobtain pellets. The obtained pellets had a melt index (MI) of 2.5 g/10minutes.

The above polymer was decomposed with a peroxide to obtain a lowmolecular weight polymer. The obtained low molecular weight polymershowed no change in the pentad fraction, the peak temperature ofmelting, or the enthalpy of melting from those of the original polymer.

Preparation Example 2 (1) Preparation of a Magnesium Compound

Into a glass reactor which had an inner volume of about 6 liters, wasequipped with a stirrer, and had been sufficiently purged with nitrogengas, about 2,430 g of ethanol, 16 g of iodine, and 160 g of magnesiummetal were placed. The obtained mixture was heated while being stirredto allow the reaction to proceed in the mixture under a refluxingcondition until hydrogen gas was not generated any more in the reactionsystem, and a solid reaction product was produced. By drying theobtained reaction mixture containing the solid reaction product under avacuum, a magnesium compound was obtained.

{2} Preparation of a Solid Catalyst Component of Component (a)

Into a glass reactor which had an inner volume of 5 liters and had beensufficiently purged with nitrogen gas, 160 g of the above magnesiumcompound obtained in (1) (not pulverized), 800 ml of purified heptane,24 ml of silicon tetrachloride, and 23 ml of diethyl phthalate wereplaced, and the reaction system was kept at 80° C. While the reactionsystem was stirred, 770 ml of titanium tetrachloride was added into thesystem, and the reaction was allowed to proceed at 110° C. for 2 hours.Then, the solid component was separated and washed with purified heptaneat 90° C. To the washed solid component, 1,220 ml of titaniumtetrachloride was added, and the reaction was allowed to proceed at 110°C. for 2 hours. The solid component was washed sufficiently withpurified heptane to obtain a solid catalyst component of component (a).

(3) Gas Phase Polymerization

Into a polymerization reactor having an inner volume of 200 liters,components were supplied at the following rates: the above solidcatalyst component of component (a) obtained in (2), 6.0 g/hour;triisobutylaluminum (TIBA), 0.2 mol/hour; 1-allyl-3,4-dimethoxybenzene(ADMB), 0.012 mol/hour; diphenyldimethoxysilane (DPDMS), 0.005 mol/hour;and propylene, 37 kg/hour. The first stage polymerization was allowed toproceed at 70° C. and 28 kg/cm²G. The rate of formation of the polymerwas 30 kg/hour.

The polymer obtained by the first stage polymerization was continuouslytransferred to a polymerization reactor of the second stage. Thepolymerization was allowed to proceed at 50° C. and 15 kg/cm2G whileethylene was supplied at 15 kg/hour and propylene was supplied at 5kg/hour, and a polymer powder containing 16.5% by weight of the ethyleneunit was obtained with a conversion of 40% in the second stage.

The polymer obtained by the above first stage polymerization was ahomopolymer of propylene having an intrinsic viscosity [η] (135° C., indecaline) of 4.27 dl/g.

The above homopolymer contained 60.0% by weight of a fraction insolublein boiling n-heptane which had [η] of 4.76 dl/g and a fraction solublein boiling n-heptane which had [η] of 2.65 dl/g.

The homopolymer had a pentad fraction expressed by rrrr/(1−mmmm)×100 of34.5% as calculated from ¹³C-NMR, a peak temperature of melting (Tm) of158° C. as measured by DSC, and an enthalpy of melting (ΔH) of 54J/g asmeasured by DSC. With respect to the head-to-tail bonding of propylene,no reversed bonding was found.

The polymer obtained by the second stage polymerization is described inthe following. This polymer was a flexible polypropylene resincomprising the homopolymer of propylene and a random copolymer ofethylene and propylene.

The polymer obtained by the two-stage polymerization had an intrinsicviscosity [η] of 4.77 dl/g. To powder of the obtained polymer,2,5-dimethyl-2,5-di(t-butylperoxy)-hexane was mixed, and then anantioxidant, a heat stabilizer, and a chlorine scavenger were added. Theobtained mixture was extruded through a 40 mmφ extruder to obtainpellets. The obtained pellets had a melt index (MI) of 2.0 g/10 minutes.

The above polymer was decomposed with a peroxide to obtain a lowmolecular weight polymer. The obtained low molecular weight polymershowed no change in the pentad fraction, the peak temperature ofmelting, or the enthalpy of melting from those of the original polymer.

This polymer had a tensile modulus of 230 MPa.

EXAMPLE 4

A Decorative Building Material Having a Stone Grain Pattern

(1) Preparation of a Material of a Surface Layer

The pellets of the homopolymer of propylene obtained in PreparationExample 1 in an amount of 90% by weight and 10% by weight of chips ofpolyethylene terephthalate were mixed together using mixing rolls at aroll temperature of 170° C. for 5 minutes, and a sheet having athickness of 200 μm was prepared.

(2) Preparation of a Backing Material

A mixture containing 20% by weight of the flexible polypropylene resinobtained in Preparation Example 2, 18% by weight of SBR (manufactured byASAHI CHEMICAL INDUSTRY Co., Ltd.; trade name, TUFDEN 2003), 2% byweight of SEBS (manufactured by ASAHI CHEMICAL INDUSTRY Co., Ltd.; tradename, TUFTEC H-1051), 45% by weight of aluminum hydroxide (manufacturedby SHOWA DENKO K.K.; trade name, HISILITE H-21), and 15% by weight ofcalcium carbonate was kneaded at a set temperature of 120° C. for 5minutes using a Banbury mixer, and a sheet having a thickness of 3 mmwas prepared by using mixing rolls while the thickness is adjusted bythe rolls.

(3) Preparation of a Laminated Sheet

A laminated sheet was prepared by laminating the sheets obtained in (1)and (2) using a press molding machine at a set temperature of 200° C. toobtain a decorative building material having a stone grain pattern.

Physical properties and feel of the obtained material are shown in Table2.

EXAMPLE 5

A Decorative Building Material of a Sliced Tile Type

(1) Preparation of a Material of a Surface Layer

The homopolymer of propylene obtained in Preparation Example 1 wasplaced into a specific mold and formed by press molding at a settemperature of 200° C. to obtain a plate having a thickness of 50 mm. Bycutting the obtained plate, a sheet having a thickness of 200 Am wasprepared.

(2) Preparation of a Backing Material

A sheet having a thickness of 2 mm was prepared in accordance with thesame procedures as those conducted in Example 4 (2).

(3) Preparation of a Laminated Sheet

A laminated sheet was prepared by laminating the sheets obtained in (1)and (2) using a press molding machine at a set temperature of 180° C. toobtain a decorative building material of a sliced tile style.

Physical properties and feel of the obtained material are shown in Table2.

EXAMPLE 6

A Decorative Building Material Having a Marble Pattern

(1) Preparation of a Material of a Surface Layer

The homopolymer of propylene obtained in Preparation Example 1 in anamount of 90% by weight and 10% by weight of a pigment (a mixture of anorganic pigment and an inorganic pigment) were placed into a hopper, andthe obtained mixture was formed by injection molding at a settemperature of 220° C. to prepare a sheet having a thickness of 1 mm.

(2) Preparation of a Backing Material

A sheet having a thickness of 3 mm was prepared in accordance with thesame procedures as those conducted in Example 4 (2).

(3) Preparation of a Laminated Sheet

A laminated sheet was prepared by laminating the sheets obtained in (1)and (2) using a press molding machine at a set temperature of 180° C. toobtain a decorative building material having a marble pattern.

Physical properties and feel of the obtained material are shown in Table2.

EXAMPLE 7

A Decorative Building Material of a Back Printed Type

(1) Preparation of a Material of a Surface Layer

Pellets of the homopolymer of propylene obtained in Preparation Example1 was formed to a sheet having a thickness of 200 μm in accordance withthe cast molding, and a pattern was formed on one face of the obtainedsheet by printing.

(2) Preparation of a Backing Material

A sheet having a thickness of 3 mm was prepared in accordance with thesame procedures as those conducted in Example 4 (2).

(3) Preparation of a Laminated Sheet

A laminated sheet was prepared by laminating the sheets obtained in (1)and (2) using a press molding machine at a set temperature of 180° C. toobtain a decorative building material of a back printed type.

In the above material, the two sheets were laminated together in such amanner that the sheet obtained in (2) was attached to the printed faceof the sheet obtained in (1). The lamination could be conducted moreeasily when an adhesive or a primer was used.

Physical properties and feel of the obtained material are shown in Table2.

EXAMPLE 8

A decorative Building Material of a Back Printed Type

A decorative building material of a back printed type was prepared inaccordance with the same procedures as those conducted in Example 7except that a mixture of 90% by weight of the homopolymer of propyleneobtained in Preparation Example 1 and 10% by weight of a hydrogenatedSBR (manufactured by JSR Co., Ltd.; trade name, DYNARON 1320P) was usedin place of the pellets of the homopolymer of propylene used in Example7 (1). Physical properties and feel of the material are shown in Table2.

Comparative Example 2

A Floor Material Made of Polyvinyl Chloride

(1) Preparation of a Material of a Surface Layer

A polyvinyl chloride resin (degree of polymerization, 700) in an amountof 100 parts by weight and 40 parts by weight of dioctyl phthalate asthe plasticizer were kneaded together using mixing rolls, and a sheethaving a thickness of 200 μm was prepared. A pattern was formed on oneface of the obtained sheet by printing.

(2) Preparation of a Backing Material

A sheet having a thickness of 3 mm was prepared in accordance with thesame procedures as those conducted in Example 4 (2).

(3) Preparation of a Laminated Sheet

A laminated sheet was prepared by laminating the sheets obtained in (1)and (2) using a press molding machine at a set temperature of 180° C. toobtain a floor material made of a polyvinyl chloride resin.

In the above material, the two sheets were laminated together in such amanner that the sheet obtained in (2) was attached to the printed faceof the sheet obtained in (1).

Physical properties and feel of the obtained material are shown in Table2.

TABLE 2 abrasion heat weather- resistance resistance ability feelExample 4 ∘ ∘ ∘ ∘ Example 5 ∘ ∘ ∘ ∘ Example 6 ∘ ∘ ∘ ∘ Example 7 ⊚ ∘ ∘ ∘Example 8 ∘ ∘ ∘ ∘ Comparative Example 2 Δ Δ Δ Δ

The homopolymer of propylene which was obtained in Preparation Example 1(PP of Prep.Ex.1) and used as the material of the surface layer in thedecorative building material of the present invention was superior toconventional polypropylenes as shown in the following. Films having athickness of 100 μm were prepared for the comparison. As theconventional polypropylene, a homopolymer of propylene (homoPP), a blockcopolymer of propylene (blockPP), and a random copolymer of propylene(randomPP) were used.

(1) Superior to homoPP with respect to flexibility

tensile modulus (MPa):

homoPP=about 1000

PP of Prep.EX.1=500

(2) Superior to blockPP with respect to transparency

haze (%):

blockPP=about 40

PP of Prep.Ex.1=about 7

(3) Superior to randomPP with respect to heat resistance

melting point measured by DSC (° C.): randomPP=about 120° C.

INDUSTRIAL APPLICABILITY

The decorative film or sheet of the present invention has a surfacelayer showing excellent transparency and hardness, shows excellentworkability in V-cutting, lapping, and vacuum molding, and does notcause problems in disposal because chlorine gas is not formed byincineration. Thus, the film or the sheet is valuable as a commercialproduct.

The decorative film or sheet of the present invention can beadvantageously used, for example, for materials of furniture, cabinetsof refrigerators and televisions, and interior materials of buildingsbecause of the above advantageous properties.

The decorative building material of the present invention showsexcellent heat resistance, weatherability, and abrasion resistance andhas a property for printing and a workability in fabrication(workability in V-cutting and vacuum molding) as excellent as those ofbuilding materials made of polyvinyl chloride resins. The decorativebuilding material of the present invention provides soft feeling anddoes not cause problems in environment. Therefore, this material isadvantageously used for floor materials and decorative wall materials.

What is claimed is:
 1. A decorative film or sheet having a laminatestructure comprising a surface layer, an adhesive layer, and a layerhaving a pattern, wherein the surface layer is made of a film or a sheetcomprising a resin which comprises (A) 100 to 60% by weight of apolypropylene resin comprising one or both of a homopolymer of propyleneand a copolymer of propylene containing 4% by weight or less of units ofother olefins, the homopolymer and the copolymer having (i) a pentadfraction expressed by rrrr/(1−mmmm)×100 of 15 to 60% as measured by anuclear magnetic resonance spectrum of an isotopic carbon (¹³C-NMR),(ii) a peak temperature of melting (Tm) of 150° C. or higher as measuredby a differential scanning calorimeter (DSC), and (iii) an enthalpy ofmelting (ΔH) of 100 J/g or less as measured by DSC, and (B) 0 to 40% byweight of a thermoplastic elastomer copolymer.
 2. A decorative film orsheet according to claim 1, wherein the homopolymer and the copolymerhave (i) a pentad fraction expressed by rrrr/(1−mmmm)×100 of 15 to 50%as measured by a nuclear magnetic resonance spectrum of an isotopiccarbon (¹³C-NMR).
 3. A decorative film or sheet according to claim 1,wherein the homopolymer and the copolymer have [iii] an enthalpy ofmelting (ΔH) of 10 to 100 J/g.
 4. A decorative film or sheet accordingto claim 1, wherein the resin contains a thermoplastic elastomercopolymer which is at least one copolymer selected from the groupconsisting of elastomers of copolymers of ethylene and α-olefins having3 or more carbon atoms, elastomers of copolymers of ethylene, α-olefinshaving 3 or more carbon atoms, and dienes, elastomers of copolymers ofstyrene and dienes, and elastomers of hydrogenated copolymers of styreneand dienes.
 5. A decorative film or sheet according to claim 1, whereinthe layer having a pattern has a two-layer structure comprising apatterned layer and a shielding layer.
 6. A decorative materialcomprising the decorative film or sheet described in claim 1 which isbonded to a substrate selected from the group consisting of woodsubstrates, metal substrates, inorganic substrates, and resinsubstrates.
 7. A method of making a decorative film or sheet, the methodcomprising laminating a surface layer, an adhesive layer, and a layerhaving a pattern; and producing the decorative film or sheet having alaminate structure of claim
 1. 8. A decorative film or sheet having alaminate structure comprising a surface layer, an adhesive layer, alayer having a pattern, an adhesive layer, and a substrate, wherein thesurface layer or the surface layer and the substrate are made of a filmor a sheet comprising a resin which comprises (A) 100 to 60% by weightof a polypropylene resin comprising one or both of a homopolymer ofpropylene and a copolymer of propylene containing 4% by weight or lessof units of other olefins, the homopolymer and the copolymer having (i)a pentad fraction expressed by rrr/(1−mmmm)×100 of 15 to 60% as measuredby a nuclear magnetic resonance spectrum of an isotopic carbon(¹³C-NMR), (ii) a peak temperature of melting (Tm) of 150° C. or higheras measured by a differential scanning calorimeter (DSC), and (iii) anenthalpy of melting (ΔH) of 100 J/g or less as measured by DSC, and (B)0 to 40% by weight of a thermoplastic elastomer copolymer.
 9. Adecorative film or sheet according to claim 8, wherein the homopolymerand the copolymer have (i) a pentad fraction expressed byrrrr/(1−mmmm)×100 of 15 to 50% as measured by a nuclear magneticresonance spectrum of an isotopic carbon (¹³C-NMR).
 10. A decorativefilm or sheet according to claim 8, wherein the homopolymer and thecopolymer have [iii] an enthalpy of melting (ΔH) of 10 to 100 J/g.
 11. Adecorative film or sheet according to claim 8, wherein the resincontains a thermoplastic and the copolymer which is at least onecopolymer selected from the group consisting of elastomers of copolymersof ethylene and α-olefins having 3 or more carbon atoms, elastomers ofcopolymers of ethylene, α-olefins having 3 or more carbon atoms, anddienes, elastomers of copolymers of styrene and dienes, and elastomersof hydrogenated copolymers of styrene and dienes.
 12. A decorative filmor sheet according to claim 8, wherein the layer having a pattern has atwo-layer structure comprising a patterned layer and a shielding layer.13. A decorative material comprising the decorative film or sheetdescribed in claim 8, which is bonded to a substrate selected from thegroup consisting of wood substrates, metal substrates, inorganicsubstrates, and resin substrates.
 14. A method of making a decorativefilm or sheet, the method comprising laminating a surface layer, anadhesive layer, a layer having a pattern, an adhesive layer, and asubstrate layer; and producing the decorative film or sheet having alaminate structure of claim
 8. 15. A decorative building material havinga surface layer comprising a resin which comprises (A) 100 to 60% byweight of a polypropylene resin comprising one or both of a homopolymerof propylene and a copolymer of propylene containing 4% by weight orless of units of other olefins, the homopolymer and the copolymer having(i) a pentad fraction expressed by rrrr/(1−mmmm)×100 of 15 to 60% asmeasured by a nuclear magnetic resonance spectrum of an isotopic carbon(¹³C-NMR), (ii) a peak temperature of melting (Tm) of 150° C. or higheras measured by a differential scanning calorimeter (DSC), and (iii) anenthalpy of melting (ΔH) of 100 J/g or less as measured by DSC and (B) 0to 40% by weight of a thermoplastic elastomer copolymer.
 16. Adecorative building material according to claim 15, wherein thehomopolymer and the copolymer have (i) a pentad fraction expressed byrrrr/(1−mmmm)×100 of 15 to 50% as measured by a nuclear magneticresonance spectrum of an isotopic carbon (¹³C-NMR).
 17. A decorativebuilding material according to claim 15, wherein the homopolymer and thecopolymer have (iii) an enthalpy of melting ΔH of 10 to 100 J/g.
 18. Adecorative building material according to claim 15, wherein the resincontains a thermoplastic elastomer copolymer is at least one copolymerselected from the group consisting of elastomers of copolymers ofethylene and α-olefins having 3 or more carbon atoms, elastomers ofcopolymers of ethylene, α-olefins having 3 or more carbon atoms, anddienes, elastomers of copolymers of styrene and dienes, and elastomersof hydrogenated copolymers of styrene and dienes.
 19. A decorativebuilding material according to claim 15, wherein the surface layer is asheet having print at least on one face, a sheet containing chips of atleast one material selected from the group consisting of syntheticresins and rubbers, or a sheet containing a coloring agent.
 20. Adecorative building material according to claim 15, wherein an adhesivelayer is disposed between the surface layer and the backing material.21. A method of making a decorative building material, the methodcomprising laminating a surface layer and a backing material; andproducing the decorative building material of claim
 15. 22. A decorativebuilding material according to claim 15, wherein the flexiblepolypropylene resin has a tensile modulus of 600 Mpa or less.
 23. Adecorative building material according to claim 15, wherein the flexiblepolypropylene resin has a tensile modulus in the range of 300 to 400Mpa.
 24. A decorative building material according to claim 15, whereinthe flexible polypropylene resin comprises one or both of a homopolymerof propylene and a copolymer of propylene containing 4% by weight orless of units of other olefins.
 25. A decorative building materialaccording to claim 15, wherein the flexible polypropylene resincomprises one or both of a homopolymer of propylene and a copolymer ofpropylene containing 4% by weight or less of units of other olefins, andwherein the homopolymer and the copolymer in the flexible polypropyleneresin have: (i) a pentad fraction expressed by rrrr/(1−mmmm)×100 of 15to 60% as measured by a nuclear magnetic resonance spectrum of anisotropic carbon ¹³C-NMR, (ii) a peak temperature of melting Tm of 150°C. or higher as measured by a differential scanning calorimeter DSC, and(iii) an enthalpy of melting ΔH of 100 J/g or less as measured by DSC.26. A decorative building material according to claim 15, wherein theflexible polypropylene comprises a mixture of (a) and (b): (a) a randomcopolymer of propylene containing olefin units other than propylene; and(b) a polypropylene resin comprising one or both of a homopolymer ofpropylene and a copolymer of propylene containing 4% by weight or lessof units of other olefins, wherein said homopolymer and copolymer in (b)resin have: (i) a pentad fraction expressed by rrrr/(1−mmmm)×100 of 15to 60% as measured by a nuclear magnetic resonance spectrum of anisotropic carbon ¹³C-NMR, (ii) a peak temperature of melting Tm of 150°C. or higher as measured by a differential scanning calorimeter DSC, and(iii) an enthalpy of melting ΔH of 100 J/g or less as measured by DSC.